Skip to main content

Full text of "Hand-book of chemistry"

See other formats


Google 



This is a digital copy of a book that was preserved for generations on library shelves before it was carefully scanned by Google as part of a project 

to make the world's books discoverable online. 

It has survived long enough for the copyright to expire and the book to enter the public domain. A public domain book is one that was never subject 

to copyright or whose legal copyright term has expired. Whether a book is in the public domain may vary country to country. Public domain books 

are our gateways to the past, representing a wealth of history, culture and knowledge that's often difficult to discover. 

Marks, notations and other maiginalia present in the original volume will appear in this file - a reminder of this book's long journey from the 

publisher to a library and finally to you. 

Usage guidelines 

Google is proud to partner with libraries to digitize public domain materials and make them widely accessible. Public domain books belong to the 
public and we are merely their custodians. Nevertheless, this work is expensive, so in order to keep providing tliis resource, we liave taken steps to 
prevent abuse by commercial parties, including placing technical restrictions on automated querying. 
We also ask that you: 

+ Make non-commercial use of the files We designed Google Book Search for use by individuals, and we request that you use these files for 
personal, non-commercial purposes. 

+ Refrain fivm automated querying Do not send automated queries of any sort to Google's system: If you are conducting research on machine 
translation, optical character recognition or other areas where access to a large amount of text is helpful, please contact us. We encourage the 
use of public domain materials for these purposes and may be able to help. 

+ Maintain attributionTht GoogXt "watermark" you see on each file is essential for in forming people about this project and helping them find 
additional materials through Google Book Search. Please do not remove it. 

+ Keep it legal Whatever your use, remember that you are responsible for ensuring that what you are doing is legal. Do not assume that just 
because we believe a book is in the public domain for users in the United States, that the work is also in the public domain for users in other 
countries. Whether a book is still in copyright varies from country to country, and we can't offer guidance on whether any specific use of 
any specific book is allowed. Please do not assume that a book's appearance in Google Book Search means it can be used in any manner 
anywhere in the world. Copyright infringement liabili^ can be quite severe. 

About Google Book Search 

Google's mission is to organize the world's information and to make it universally accessible and useful. Google Book Search helps readers 
discover the world's books while helping authors and publishers reach new audiences. You can search through the full text of this book on the web 

at |http: //books .google .com/I 






'"'4 



„ WILLIAM O HAY. 
Of BoMon, Mh»s. 



<ciaH at ittan.) X j 

Rf ceiled /fv^/OfcAy, ^V 

K, /SiO. ■■'J* 



WORKS 



CAVENDISH SOCIETY. 



FOUNDED 184S. 



HAND-BOOK 



OF 



CHEMISTRY 



BY 

LEOPOLD GMELIN. 



VOL. XL 



ORGANIC CHEMISTRY, 

VOL. V. 

01U3ANIC COMPOUNDS CONTAININO TEN AND TWELVE ATOMS OF CABBON. 



TRANSLATED BY 

HENRY WATTS, B.A., RC.S, 



O LONDON: 
PRINTED FOR THE CAVENDISH SOCIETY, 



MDCCCLVII. 



KPE zsjr 



CONTENTS OF VOL. XI 



(VOL. V. OF ORGANIC CHEMISTRY.) 



TEN-CARBON COMPOUNDS {continued), 

Amtlbnb Sskiss. 

Primary Nueieui : Amylene, C***!!**. 

Page 

Amylenef C^^H** .... .... .... .... .... .... 1 

Amyl, C»«H" or C»H"' .... 3 

Ethamyl, C^HW - C«H«,CWH» 5 

Bntamyl, CMH» - C8H»,CWH" 5 

Hydride of Amyl, C^H" .... 6 

Oxide of Amyl or AmyUc ether, CMH"0 .... .... .... 7 

Methamylic ether, C^B}H>* = C«H»,CWH»,02 8 

Vinamyllc ether, CMRIH)* « C*H»,CWH",0« 8 

AmyUc Alcohol, C»H«0> 9 

Valeraldide, C»HM0» 17 

Valeraldide-ainmoiiia, NH»,CW>ff«0« 19 

Valeraldide with Bianlphite of Soda, C")Hi<O>,Na0,2S0> + 2 Aq. 19 

Metaraleraldide ? .... .... .... .... .... .... 20 

Valerianic add, C^B}H)* .... .... .... .... .... 21 

Bihydrated Valerianic acid, Ci0Hi<O«,2HO 29 

Valerate of Ammonia .... .... .... .... .... 30 

Valerate of Potaah, C*0H»KO< .... .... .... .... 31 

Valerate of Soda .... .... .-.. .... .... 31 

Valerate of Baryta, C»»H«BaO* .... .... .... 32 

Valerate of Strontia .... .... .... .... .... 32 

Valerate of lime, C^^H'CaO* .... .... .... .... 33 

Valerates of Magnesia, Glncina, Almnina, Zirconia, Uraniam, 

Manganese, Bismuth, Zinc and Cadmiom .... .... 33, 34 

Valerate of Lead. — a. Tribasic, 2PbO,C><^H<^PbO<. b. Mono- 

basic, C><>H»PbO< .... .... .... .... .... 34 

Ferrous Valerate .... .... .... .... .... 35 

Ferric Valerate.— a. Mono-add ? Pc»O»,C»0H»«O^— *. Bi-add ? 

FeW,2C>«HM0*.— c. WHh excess of add .> 35 

Valerates of Cobalt, Nickel, Copper, and Mercury .... .... 36 

Valerate of Sttver, C»"H»AgO* .... .... .... .... 86 



VI 



CONTENTS. 



Page 

Anhydrous Valerianic acid, CWH^O^ or (C^oHflO^y^O- ... .... 37 

Sulphideof Amyl, C»«H"S .... .... .... 38 

Amylic Mercaptan, C'0H»2S» .. .... .... .... .... 38 

Biaulphideof Amyl.' Ci»H'»S2 40 

Iodide of Amyl, C^H"! 41 

Bromide of Amyl, C»»H»Br 42 

Chloride of Amyl, C^H^Cl 42 

Chloramylal ... . ... .... .... 43 

Telluramyl, C><'H»Tc 44 

Cof^ngated compound* of the Primary Nucleus, C^**H*". 

Carbonate of Amyl, CWH"0,C02 . .... ... 45 

Tribaaic Borate of Amyl, 3C»0H»O,BO3 46 

Biborate of Amyl, CWH"0,2B03 . .. 47 

Phosphite of Amyl, 2C»"H"0,PHCH 47 

Amylophoiphorous acid, CWH"P06 = C»0H«O2.PHO< 48 

Amylophosphoricacid, C>0H"PO8 = C»»Hi202,PHO« 49 

Amylophosphates = C^OH^APPO^ = C»«H»0M2O2,PflO« 50 

AmyloBulphurous acid, CWH»2S«0« = CWH«0«,2S02 50 

Amylosulphitei - CioH»'MS20« = Ci«H"MO«,2S02 ... 53 

Amylosulphmic acid, CioHiss^O^ = C>0Hi«O2,2SO» 55 

Amylosnlphate of AmmonU, C^H"(NH<)S208 56 

Amylosulphate of Potash, CWH"KS20« .... 56 

AmyloBulphatc of Soda, CWH^NaS^O^ .... 56 

Amylosulphate of Baryta, C»0H"BaS«O8 + Aq and + 2Aq 57 

Amylosulphate of Strontia, C*«H"SrS208 + 2Aq .... 67 

Amylosulphate of Lime, C»0H"CaS2O» + Aq ... .... 57 

Amylosulphates of Magnesia and Alumina .... .... .... 58 

Amylosulphate of Manganese, C^^Ii^MgS-OS + 4Aq .... 59 

Amylosulphate of Zinc, Ci0H»ZnS2O8 + 2Aq .... 59 

Amylosulphate of Lead. — a. Bibasic— J. Monobasic, C^^H^PhS^O^ 59 

Amylosulphates of Iron, Cobalt and Nickel .... .... 59 

Cupric and Mercuric Amylosulphates.... .... ... .... 60 

Amylosulphate of Silver, C^OH^iAgS^O* .... .... .... 60 

Amyloxanthic add, C^^HWO^S^ « Ci0H>2O2,2CS« 60 

Amyloxanthate of Ammonia, Ci«H"(NH^)0^2CS' ... .... 61 

Amyloxanthate of Potash, C»«H"K02,2CS2 .... .... .... 61 

Amyloxanthate of Lead .... .... .... .... .... 61 

Methamylic and Vinamylic Oxysulphocarbonates : C'H3,C»0H",2CS2O 

and C*Hs,CWH»,2CS?0 62 

Bioxysulphocarbonate of Amyl, C»H"0«S< = C'0H"O«,2CS2 .... 62 

Nitriteof Amyl, C»ni»0,N03 63 

Nitrate of Amyl, C»oH"0,NO« .... .... .... .... 64 

Bibasic SUicate of Amyl, 2CWH"0,Si02 .... ... ... ... 65 

Formiate of Amyl, Ci*n'«a^ = C»"H"0,C-II03 66 

Chloroformiate of Amyl, Ci^H'^ClQ^ = C»«H»H),C2Cia^ 66 



CONTENTS. 



Vll 



Page 

Valerate of Methyl, CWH^^O* = C?n^O,O^H^O^ .... . . 67 

Cyanide of Amyl, C^'^NH" = C»»H»o,C^NH = C'OH",C?N 67 

Sulphocyanideof Amyl, C»2NH»S2 = CWHWC2NHS2 .... .... 68 

Acetate of Amyl, C"H"0^ = CWH"0,C*H303 69 

Chloracetate of Amyl, C^*Cim^O* = Ci«H"0,C*C12H0» . . 70 

Valerate of Ethyl, Ci*H"0* = C^HSO.CWHSQS 71 

Oxalate of Amyl, C»*H«08 -= 2CWH»0,C*0« 72 

Amyloxalic acid, C"H»208 = CWHWO»,C^O« 73 

Amyloxalate of Potash.— Amyloxalate of Lime, C"H"CaO^ + 2Aq. 

Amyloxalate of Silver, C"H"Ag08 .... .... .... 73 

AUophanate > (Cyanurate) of Amyl, C"N2H"0« 74 

Monovalerin, Ci«Hi«08 = CfiK^O^.a^UKfi 75 

Bivalerin, CWH«0»» = CH806.(C»m802)2 76 

Trivalerin, CWHkq" = O»H8O«,(C»0H8O2/ 76 

Delphinin or Phocenin, C«H«0" ? .... .... .... .... 77 

Valcrone, C^W^G^ = Om^^(y,C^U^ 78 

Valeracetone, Om^Hy « C»0H»0O>,CSH2 79 

Amylomalic acid, C^H«O»0 = CWH«02,C8H^OS .... .... 79 

Amylomalate8, Ci«H"M02,C8H^08 79 

Amylotartaric add, Ci8H»fiO»2 = C^OHi202,C8H^O»o gQ 

Amylotartrate of Potash, am^^K0^,C?n*O^, and + 2Aq 81 

Amylotartrate of Soda, O0H»iNaO2,C«HW» .... .... 81 

Amylotartrate of Baryta, CWH^BaO^C^H^O'o, and + 2Aq 82 

Amylotartrate of Lead.— Amylotartrate of Silver, C'H^AgO^jC^H^O^" 82 

Valerate of Amyl, C»R»0* = C»m»0,CWH90» .... ... 83 

Oxygen-nucleus C^^^II^O^, 

Pyrotartaric Acid, C»0H»O« = C»0HW,O« .... .... 83 

Pyrotartrates of Ammonia : 

fl. C»0H«(NH<)2O8.— d. C»H7(NH^)08 87 

Pyrotartratei of Potash : 

fl. CWH6K208 + 2Aq and 4Aq. — b. C^m^KQ^ 88 

Pyrotartrate of Soda : 

a. CWH6Na208 + 6Aq and 12Aq. — *. C>»H7Na08 .... 89 
Pyrotartrate of Baryta : 

a. CWH6Ba20« + 4Aq.-6. CWH^BaQS + 2Aq 90 

Pyrotartrate of Strontia : 

a. C'^'HSSr^OS + 2Aq. -6. C^OH^SrO* + 2Aq .. . 90 
Pyrotartrate of Lime : 

a. C»H6Ca208 + 4Aq.— Acid salt. CiOH7CaO«,2CWH«0« + 2Aq 91 
Pyrotartrate of Magnesia : 

a. Ci*H«Mg20« + 6Aq and 12Aq.— 6. C^H^MgOS 91, 92 
Pyrotartrates of Glucina : 

Ci0H«G2O8 and CWH7G08,cw>H80« .... .... 92 

Pyrotartrates of Alumina : 

Monobasic, AlW.C'OHSO^ + 2Aq.— Acid 92 



Vlll CONTENTS. 

Page 

Uranic Pyrotartrste, CWH«(2U«0')08,2[CWH'(U202)0«] + 4Aq 92 

Pyrotartrate of Manganese, CioH^Mn^Oi + 2Aq .... .... 93 

Pyrotartrate of Bismnth, CWH«(2BPO0O8,2[C«>H7(Bi2O')O8] + 2Aq 93 
Pyrotartrates of Zinc : 

a. Polybasic — 6. Bibaaic, C«>H«Zn«08 and + 6Aq.... .... 93 

Pyrotartrates of Cadmium ; 

a. Ci*HHM>0» + 4Aqand6Aq. — 6. Monobasic .... 94 
Pyrotartrates of Lead : 

a. Sexbasic, 4PbO,CWH»Pb2C)8 94 

b. Qaadribaaic, 2PbO,C»H6Pb20« 95 

c. Bibasic, CM>H«Pb208 + 4Aq 95 

Ferrous Pyrotartrate .... .... .... .... .... 95 

Ferric Pyrotartrates : 

a. 18Fe30»,CWH«0« + 18Aq. — *. 6Fe808,CWH«0« + 6Aq. 96 

c. 4Fe>0»,3CWH«0« + 6Aq 96 

rf. FeSO»,C«>H808 + 3Aq 96 

e. Fe20»,9CWH«0« + 18Aq 97 

Pyrotartrates of Cobalt : 

a, Basic — 6. Acid .... .... .... .... . 97 

Pyrotartrates of Nickel ; 

a. C^UniiHy + 4Aq.— A. Acid, C>«HrNi09,CWH80« + 2Aq. 97 

Cupric Pyrotartrates : 

a. Quadribasic, 4CuO,CWH«0« + 4Aq .... 97 

b. Bibasic, C^OH^Cu^OS + 2Aq and 4Aq .... .... 98 

MercurouB and Mercuric Pyrotartrates .... .... .... 98 

Pyrotartrate of SUver, CWH«Ag20« .... .... ... 99 

Pyrotartrate of Methyl C"H»208 - 2C2HH),C"»H«0« .> 100 

Pyrotartrate of Ethyl, C^m^H^ ^ 2C^H60,C«»H«0« 100 

Oxygen-nucleua, C^^HW. 

Anhydrous Pyrotartaric acid, CWH«0« = Om^0\Q^ 101 

.4/ipwiM? to Pyro/aWflWc acid ; Bipyrotartramide, C*°NH W .... 102 

Chlorine^nucleus, C^^d'H'. 

TerchloroTalerianic add, C^H^l^WyO* .... .... .... .... 103 

Terchlorovalerates, C'«CI»H«M,0* . . .... .... 103 

Chlorine-nucleus, CWC1*0«. 

QuadrichloroTalerianic add, CWC1*H»,0 .... .... .... .... 103 

QuadrichloroTalerates, CoCl^^MjO* .... .... .... 104 

Amidagen'tiucleuit C^^AdH". 

AmyUmine. C»»NH" - CWAdH'.H* 105 

Carbonate. — Sulphate. — Hydrochlorate, Ci^^NH^^^HCl .... 106 

Platinum-salt, Ci<>NH",HCl,PtC12 107 



CONTENTS. IX 

Page 

BiwnylamUie, C»NHa - CWAd(C^0H")H9,H« 107 

MeteUiamyUmine, C^NHW = C«>Ad(C?H«)(C^H*)H7,H^ 108 

BieduunylamiDe, CWNH^i « CWAd(C^H*)2H7.H2 108 

Triamylamine, C*«NH» - CMAd(CWH";^H7,H2 109 

Mcthylobiethamylaminc. O^NW^ « CWAd(C2H3)(C^H«)8H«,H2 .... 110 

Platinum-salt, C^NH^ HCl,Pt(:i3 110 

TriethamylamiiMS, C^^NU^ « a^Xd{CnV)nV,n^ HI 

Hydriodate, C=2NU2i,HI. — Plaiinum-salt, C^NH»,HCl,PtC12 111 

Tetramylamine, C-»xNH« = CiOAd(C"H";3HMP 112 

Hydriodate, C«1IN*», II I. — Platinum. salt, C*'NII« I!Ci,riCl- 112 

Valeramide, C'«NU"Oa - CioAail»,0« 113 

Amylttfethane, C«NH"0< « CWAdH",2C0'^ 114 

Oxamylane, C"Nir»0'' « C'0AdIl».C^Os 1 15 

Sincalinc, C'«NH"0» = C'^Adiri.O' 115 

Gold-salt, C»Na'-30-,HCl,AuCl. — Platinum-salt, 

CMNH«0-,HCI,PtCl2 lie 

XanthamyUmide, C'SNll^S^O' » CWAdH",CS«,CO- 116 

Mercury-compound, C^^NU'^S'OMHgCl .... .... .... 113 

Amidoffen-nuclew, C»»Ad«H-'0«. 

Inosinic acid, Ci»N2H«0W =. CW»Ad2H20«,0< 119 

Inosates « C>0Nni*BaOW 120 

Axo-nucleus, O^miK 

ValeroDitrile, C^NH* .... .... .... ... .... •... 121 

Valeraoctomtrilc, C»N-H«*0« 123 

Conjugated Compound*. 

Amyl-nrca, C^N'H^H)" .... .... ...t .... .... 123 

Valeryl-urea, C"N2H«0* .... .... .... .... ... 124 

Amylo-piperidine, CMNH« = C^Hw C^NH" 124 

Appendix to the Amylene'Seriet. 

Cacodyl of Valerianic acid .... .... .... •••• ••■• 125 

Stibamylfl .... .... •••• •••• •••• •••• •••• *^^ 

Stibtriamyl. (C'«H")»Sb 126 

Oxide. — Cbloride (C>»H")3SbCP, &c 127 

Sulphate (C>«fl»)»Sb,2SO< 128 

Stibbiamyl (C*'H")'Sb .... .... .... ... ■•. 129 

Zinc-Amyl« C*"H"Zn .... .... ... ».. ••• 129 

Stannamyls .... .... .... •••• •••• •— — • 1^^ 

Biataniuunyl, C^®H"Sn° .... ... .... •••• 1^1 

Oxide, C»H"Sn20. — Chloride, CWH"Sn'Cl .... .... 131 

Stannamyl, C"H"Sn .... .... .... •••. •••• 131 

Chloride, C><>H"SnCl. — Sulphate, CWH"SiiO,SO» 131 

6 



Xli CONTENTS. 

P»ge 
Ojeyi;hlorine-nueleu9 C^Cl'HSO*. 

BieUorkiAone, CMCPEPO* « (?C1«IP0»,0« ^ 188 

Bichlorhydrokinone, C«CPH<CH = C"C1«H«0«,H«0« 189 

Chloranilic acid, C^CVU^C^ « C»CPEPO»,0« 190 

Chloraoilate of PoUsb, C"CPK?0« + 2Aq .... •... .... 191 

Chloranilate of SiWer, CUCPAgH)" 192 

Conjuffoied compounds t Bichlorkinhydrone, Ci3Cl'H^0\CiK:ra<0< .... 192 

OxycMorine-nueleuM C^Cl'HO'. 

Terchlorklnone, C»C1»H0* = CMa»H03,0» 193 

Terchlorhydrokinone, CMCPft»0* = C»C1'H0MP0« 195 

Conjugated compound : Terchlorkinhydrone, Ci^l'HO^C^CPHSO^ 196 

CMorine-nucleus C^Cl^O*. 

Chloranil, C»Cl^O^ = CWCl^0»,09 :. 196 

Chlorhydranil, C"C1<BP0* - C»a*0«,H20» 199 

Sulphochlorine-nucleUM OH:m\'aO)\ 

Chlorosulphobenzcne, CMC1H<(S0-) .... .... .... .... 200 

Niiro-nucleu* C^^XH*. 

NitrobcMcnc, C«NH»0< « C»«XH» 201 

Kitrocarbolio acid, C«NH»0« « C"XH»,03 ^03 

Nitroehlorine^ucleut C^^CIH^ 

Nitrochloroniceic acid, C^NCIH^O* « C"XaH<,0* 204 

Nitrocbloroiiieeic ether, CMNCIH'QS «= C<H»0,Ci2XClH»0» .... 204 

Niiro^nucleus C^^Xm^ 

Binitrobenzene, C»N«H<0« = C»X«H* 204 

BinitPocarboUc acid, C^'N'H^OW = C«X2H^02 205 

Potassiam.salt, C»«X'H»K02 + Aq.— Barium-ialt, C^XSH^BaQS + 5Aq 207 

Lead-salts : a. PbO,C»2X«H3PbO» + 4 Aq.— i. PbO,2C^»X8H»PbO« .... 208 

Nitrobromme-nueleug C^^BrH'. 

Binitrobromoearbolic acid, Ci^N^rHSO^o » C)^0S?BrHS,O3 .... 208 

Bariam.salt, C?«N«BrH«BaO» + 4Aq 209 

Nitrochlorine-micleus C^a'H", 

NitrobichlorocarboUc acid, C«Na*HH)« - C»XC12H»,0« .... 210 

Ammonium-ialt, C»XCPH2(NH4)OS.— Potassium-salt, C»XCPKO>.... 210 

Biaitrocblorobensene, CWN«CIHW = C»*X«C1H» 211 



CONTENTS. nil 

Page 
Niiro-nueleui C"X»I1». 

TcraihPocarbolic or Picric acid, C'^N^HK)" « 0^nV,0^ .... 211 

Picrate of Ammonia .... .... .... .... .... 220 

Picrate of Potash, C^XmsKO* 220 

Picrate of Soda. — Picrate of Baryta, a. BaO,C"X5Il»BaO». — 

&. CWX»a2Ba03 + 5Aq .... 221 

Picrate of StrontU, C"N5H2SrO> + 5Aq .... .... .... 222 

Picrates of Lime and Magnesia .... .... .... .... 222 

Picrate of Manganese, Ci^X'H^MnO^ ^ Aq .... .... 222 

Picrate of Zinc, C^Xm^ZnO^ + OAq .... .... .... 223 

Picratcs of Lead.— a. AVhO,O^XHVVbCfi ;— ^. 2PbO,C"X»H2Pb02 
and + 3Aq;— c. PbCC^^X'H^PbO*. 

d. C«X'H2Pbp2 + Aq .... 224 

Picrateof Cobalt, C^^XnPPbO' + 5 Aq 225 

Picrate of Nickel, C»X»H«NiO« + Aq 226 

Picrate of Copper, C»»X»H«CuC)2 + 5Aq .... .... .... 226 

Mercaroos Picrate,' C^^X'Hnig^O' + 5Aq.— Mercnric Picrate 227 

Picrate of SUver, C»N»H«AgO» 227 

Picnc £ther .... .... .... .... .... «... 227 

Jl/ip«ni2ijr fo Ptcrte act(7 : Temitrocresylic acid, C^^X'H^O^ .... ..... 228 

S^phnic acid, C»«N'H»0»« « CMX»H»,0* , 228 

Styphnate of Ammonia :—«. NH»,C»«X5H2(NH^)0*.— 

6. C»»X»H«(NH«)0« 231 

Styphnate of Pota8h.-a. KO^O^^H^KO^—b. C»«X"H>KO< + 2Aq 232 

Styphnate of Soda, NaO,C»X»H2NaO* + 5Aq 232 

Styphnate of Baryta, BaO,Ci3X3U2BaO« + 3Aq .... .... 232 

Styphnate of Strontia, SrO.C^'H^SrO^ -h 4Aq .... .... 233 

Styphnate of Lime, CaOfC^m^CaO^ + 4Aq .... .... 233 

Styphnates of Magnesia, Manganese and Cadmium .... .... 233 

Styphnate of Lead, 3 PbO,C>sX«H2PbCH + 2 Aq 244 

Styphnates of Iron, Cobalt, and Nickel ..,. .... .... 234 

Styphnate of Copper, CaO,Ci^'H%aC)^ -I- 2Aq .... .... 234 

Styphnate of Copper and Ammonium, —Styphnate of Copper and 

Potassium, CuO,C*XSH'KO« + 4Aq .... .... .... 235 

Styphnate of Silver, AgO,C>^*H<AgO^ 235 

JfitroehUniM-nuekuM C^'HKn. 

CMoropicsryl, C»N»H«C10« « C»X»H«Cl 235 

Amidofftn-nucUui C^KAUK 

Solphophenylamide, Ci'NH'S'O « Ci>AdH<,SSO« 236 

Amidogen-nuchuB C^Ad'U^ 

« 

Btihbbenzolic acid, CWN^H'S^O" « C«Ad^HS4S0» 237 

Bithiobensolates, Ct3Ad3H2Ais,4SO' 237 



XIV CONTENTS. 



Page 



Amidogen-nneleus C»AdBi«HO>. 

BromanUic acid, C»AdBi»H03,0« 238 

AmidoffeH-nueleui C*<Ad^BrSO>. 

Bromamlamide, CUAd>BrSO>,0> 239 

AmidoffeMiMeleui C^AdCmoa. 

Chloranflamic «cid/C»Ada«HO»,0* 239 

Ammoniam.ialt, C"AdCP(NH<)0« 241 

SUver-ialt, CMAdCTAgO* 242 

AnUdoffen-nveleui C^^AdHTPO*. 

Chlortniltmide, C"A^C3W,0» _ 242 

JmidogefHiuehH9 C^>AdHs. 

Picramic add, C»N>HK)w - CnX«AdH»,0« 243 

Ficramate of Ammonia, CuXUdH*(NH<)OS 244 

Picramate of Potash, C»X«AdH«K,0» 244 

Picramate of Baryta, C»X»AdH«Ba.O» 244 

Picramate of Lead.^Picramate of Copper, C%<AdH*Cii,0* .... 245 

Picramate of SUver, CMX»AdH«Ag,08 245 

Atrndogen-nuekui Ci>X*AdIP. 

Ficramide, CWNWOM - CJfX»AdHa ., 245 

Ato-nueleui C^^NH*. 

Aniline, CWH' - C*^H*,H« .... .... .... .... 246 

Ordinary Phosphite : Bibasic, 2ai^H*0,HO, ePO* .... .... 256 

Monobasic, CMNH«0,2H0, cPO» 257 

Pyrophosphate, C"NH»0,H0, 6FO» .... .... .... 257 

Metaphosphate, C^^NH^O, «P0* .... .... .... 257 

Snlphite.— Sulphate, Ci^H7,UO,SO* .... .... .... 258 

Hydriodatc, C»*NHMII.— Hydrobromate .... .... 258 

Hydrochloratc, C»>NH7,HC1.— Nitrate 259 

Flnoride of Silicinm with Aniline »... .... .... 259 

Solphate of Copper with Aniline (Sulphate of Cupranilium) 

CMNH7Cu,S0* .... .... .... .... .... 260 

Mercury^mpounds : C"NH7Hg,a and C»NU7HgCl,2Hga 261 

Gold-compound.— Platinum-compound, C^HBCl,PtCl* .... 261 

Sulphocyanate, C"NH',C«NHS« .... .... .... .... 262 

Acetate.— OxaUte, 2C«NH7,C*IP08 262 

MeUiUte, Ci^H7,CS£P0S.— Butyrate, Succinate, Tartrate, Solpho- 

bensolate, C»H*(C*n>fH^,2SO>.— Picrate 263 



CONTENTS. XT 

Page 

Kcolinc, CMNH7 - C»AdH»,H« ? ^ 263 

Sulphite.— Add Sulphate, C>^H^,H0,2S0'.— Hydriodate, Hydro- 

chlorate* Nitrate .... .... .... .... .... 268 

Copper-ialti. — Mercory-salta .... .... .... .... 269 

Gold-ealts.— Platinum.salts : Chloroplatinate, C»NHK;i,PtCP 270 

Platinopicoline, CP*NH*Pt .... .... .... .... .... 271 

Acetate. — Cupro-acetate. — Oxalate. — ^Batyrate .... .... 271 

Ethylo^coline, C^fiW^ - C»aN(C*H»)H« 272 

AUfokridM rmembimp PieoUne : 

ADIHU IIC .... •>•• .... .(•• ••*• (.(• mi 9 

Oianine •«*« •••• ..«• •>.« .... .„• 274 

Anunoliiie ...• .... ••*• ...• .... ..., 276 

Mamline, C«NH«I - C»NIHM« 275 

Platinum-ialt, Ci«NIH7a,Pta« .... 277 

Biomaniliii^ C»NH«Br - CMNBrH*,BP 278 

Hydrochlorate, C^H*Br,HCl .... .... .... .... 278 

Chloroplatiiiate, C»NBrH7Cl,FtCls 279 

Oxalate, 2C»NH«Br,C<H«08 279 

Azobromne-nueleui C^Bi^H'. 

Bibromaniline, C»«NBi»H» « CWNBHH»,BP 279 

Ajsohr<mine4iueleui C^Bx'H*. 

Ttohromaailine, C"NBr»H* » C»NBr»H«,H« 280 

AzochloHne^nueleM C»NC1H<. 

Chloiaafline, CnNClH« - C»»NCIHMP 281 

Fhoq^hate.— Salphate, Ci^NClH'.HSO^.^Hydrochlomte .... 283 

Nitrate.— CUoroplatiiiate, Ci>NClH*,HCl,PtCP. 284 

Oxalate, C»NClH«,HO,C«H«0« 285 

Azochlorini-twclew Ci^NCPH*. 

Bicfaloraniline, C»NCPH< « G»NCinis,H> 285 

Tercbloraniliiie, C^C1>H« » CUNCISIP^HS 285 

Azoehiorobr(miiU'mteleu9 C»NClBi^*. 

GhloroUbiomaniline, C^NOBi^H^ » Ci>NClBi«IP,lP 286 

Axoniiroto-nuelmu C^(NO>}H^ 

Nltroaaailiiie, C»N»H«0» - C»N(NO«)HMP 287 



XVI <:ONTENTS. 

Page 
JjfonUro^,nuel€u$ C>*NXH^ 

Nitraniline, C^N^HK)^ = C^NXHMF 288 

Sulphate.— Hydrochlorate, C»3N«H«CH,HC1 .... .... 291 

Chloroplatinate : a. C»N2H«0^,HCl,PtCP.-- 

b. C»N»H«0*,HCl,2PtCP.— Oxalate, CON»HH)^H0,C*H«0«.... 291 

Azonitro.nueiett9 Ci^NX'H^ 

BinitraQilinc, C»2N»H50« « C^NXnP.lP 292 

Azotamidoffen-nucleta C^NAdH^ 

Scmibciu!i4am, C^N^IP = C"NAdH*,E2 .... 293 

AzomtroatMdogen*nueleui C^NXAdH'. 

AmidonitranUine, Ci^N^H^O^ = C«NXAdH»,H» 29$ 

Hydrochlorate, C»2N'HW,HCl 294 

Nitrate, C»N»H70*,H0,N0» 295 

Platinhydrocyanate, C'^N'HW.HCy.PtCy .... .... .... 295 

Oxalate, 2Ci2N8HW,C*H'0» 296 

Conjvgated Compounds qf 1 At. C^NH*, or a timihr mtcleu»» 

Sitlphanilic acid, C»2NIF,2SO» 296 

Sulphanilate of Ammonia, C»^H«(NH^),2SO» 297 

Sulphauilate of SoJa, C»-NH«Na,2S0» + 24 Aq 298 

Sulphanilate of Baryta, C«NH«Ba,2SO» .... .... .... 298 

Sulplianilate of Copper, C^NII»Ca,2SO' + 4Aq .., .... 298 

Sulphanilate of Silver, CMNH«Ag,2S0» 298 

Sulphanilate of Aniline .... .... .... .... .... 298 

Bisulphanilic acid, C^H7,4S03 .... .... .... .... 298 

BisulphanilateofBaryte, Ci2NH«Ba2,4SO' .... .... .... 299 

Bisulphanilate of SUvcr, C»22<»Ag2,4S09 .... .... .... 299 

Methaniline, C"NH8 = C»2(C2H3)NH*,H2 300 

FormanUide, C«NHW = C»2(C2H)AdH*.0« 300 

Anilocyanic acid, C"NH80» « C^^Cyll^.O^ 301 

CyaniUde, C"N2H« « C^^CyAdH* 303 

Aniline-urea, C^N^HSO^ « C»2CyAdH*,H203 303 

Nitranilinc-urca, C"Nm70« = C^^CyAdXH^H^O^ 304 

Ethaniline, C^NH" « C»(C<H«)NH\H2 305 

Metethaniline, C»NHW « C>2(C2H»)(C*H»)NH»,H2 306 

BiethaniUne, C»NH>* =» C«(C*H»)«NH»,H2 307 

Tricthaniline, C>*NHW = C«(C^HS)3NH«,H» 308 

Platinum-salt, C>*NU»9,HCl,PtCP .... .... .... .... 308 

Bthybromanilinc, C^NBriro = C^2(c4H*)NBrH3,H» 309 

EthychloraniUne, CWNClH^o =» C»2(C^H*)NC1H3,H* 309 

BiethychloraniUne, C^NQH" «= C»s(Cm*)2NaH3,H2 309 

Ethynitraniline, C»WH»0* ^ Cis(C*H»)NXH',HP 309 



CONTENTS. 



xvii 



Page 

OzaniUe add, C'WHW - C»(C<HO»)AdH/0< 310 

Ammonia.8aIto ! NH>,Ci«NH70« and NH>,2Ci«Niro< 311 

Barinm-salt, C>«NH«BaO«.— Caldam-salt, C"NH«CaO« .... 311 

Saver-aalt, CWNH«AgO«.--Anilinc-8iilt,C»NH7,2CWNH'0« .... 312 

Oxanilamide, CMN^H^O^ « C»2(C*H05)Ad2H»,0« 312 

Amidonitroxana, CWN»H»0» « C»(C^H0*)NXAdH«,02 313 

Amidonitroxanilic add, CWN>H70W = C»2(0»H0»)NXAd»EP,0< .... 313 

AcetonUide, CWNH»0« - C»(OHW)NH^H« 314 

Oxalunmmdc, C»N»HW « C»(0'H0*)Ad»H«,02 316 

Btttyranaide, C»NH»Oa « C^2(C8H702)NH^H2 316 

SncdnanO, C»NH»0< « C»(CPH»0»)NH40> 316 

Sacdnanilic add, C*»NH"0* « C»(C8H»0*)AdH*,0* 317 

Sttlphosacdnanil, C»NH»S»0» « C»(C8H»S»0«)NH«,0» .... 318 

Malana, C»NH»0« = C«(C»H*0*)NH*.0» 319 

MalaniUc add, C»NH"0« = C«(a»H»0*)AdH*,0< 320 

Citraoonanil, CONHW => C»2(CWH»0«)NH<,05 321 

CUraconlodanil, C«NIH«0* « (?'(CWH»0«)N1H»,0» 322 

Citracobinitranil, C»N'H70» = CM(CWH»0»)NX«H«,0« 322 

Citraconanilic add, C?2NH"0« « C«(CWH*02)AdH*,0< 323 

Itaconanilic add, C"NH"0» .... .... .... .... .... 324 

CitracoMnitraniUc add, C»N»H»0" = C»-(CWH»0»)AdX»H»,0< .... 325 

Amidonitrocitraconana, CaN»H»0« « Ci2(CWHW)NXAdH«,0» .... 326 

Pyrotartanil, CBNH»0< = C^»(CWH70»)NH^0' 326 

PyroUrtonitranil, C^N^HWO* = C»=(CWH702)NXH3,0» .... ^.. 327 

PyrotartanUic add, C^NHWQ* « C^^Om7(y)\dW,0* 328 

Pyrotartonitranmc acid, C«iy5H'K)W = C»2(CWH70«)AdXH»,0< .... 329 

AmaniUnc; C«NH»7 « C»(CWH")H^H^ 330 

MethamaniUne, C«NH» = CM(C»H")(C?H')NH>,H* 331 

EthamaniUne, O^NH" = CM(CWH")(C^H»)NH>,H« 331 

BiAmanUine, C»N1P' « C"(C»H")«,NH3,H» 332 

MetethatbaDUine, C»NH» - C«(CWH«)(C*H0(C«H>)N1P,H« .... 332 

Ethanillae-wea, C"N«H«0» - C»(C<H»)CyAdH9,IP0» 333 

Valeranilidc, C»NH»0» « C«(CMH»0»)NH\H« 333 

Biphenaniline, C»NH» - C»(C"H*)»NH«,H» 334 

Chloroplatinate, C*>NH*,HCl,PtCl> 335 

Biphenaniline with Bidiloride of PUtinnm, CWH>*,PtCP .... 335 

BipbenethaittliDe, C«NH» « Cn*(C*H«)(C»2H»)«NIP,H« .... 336 

Platiiiiim-salt, C^H^,HCl,PtCP 336 

Conjugated Comjxmndi qf2 At, C^H* or Hmilar nuclei, 

Azobenzene, CN^H^ .... •.-. .... .... ••» 337 

Benzidine, C^N'H'* = C»«N'HW IP .... .... 333 

Phosphate.— Sulphate, C»*N«H«,2HO,2SO» 339 

Hyperadd Salphate. — Hydrodilorato, CMNnI^2HCl.— Nitrate.— - 

Chloroplatinate, C«*N»H«,2HCl,2riCl^— Acetate 340 

Oxalate, C"J««U*2,C^H«08.— Tartrate 341 



XVui CONTENTS. 

Axozybenzene, C?*N^HW,02 .... ..., .... .... .... 341 

Bremaiozybeiuene, C^N'BrU^O' .... .... ..., .... 342 

Nitrazobenzcne, CWN*H»0* « C«N«XH» 343 

Nitraioxybeniene, C«N>H»0« - C»<N2XH»,0« 343 

Binitrazobexuene, C^N^HW = C^'N'X'Ha 344 

Binitrodiphenomic acid, (?*N*H»30»3 » C«X«Ad2H«,0* .... 346 

Hydrate, C*«N*H»0" + 4Aq 345 

Saver-Mlt, C«N*H"AgOi2 346 

NitroTOlphobenzeiie, C?*NH»SH)8 « C»«XH»(S02y 346 

Binitrowdphobenzenc, C«N»H8S^0» - C^Xm\SO^ .... 347 

Amidosnlphobeiizeiie, C^NH"S>0« « CMAdH>(SOS]^ 347 

Hydrochlorate, C»NH"S?0«,HC1.— Chloroplatinate, 

C»NH"S80<,HCI,PtCl« .... 348 

Biftmidoralphobenzene, C^N*H^SK>* » C^Ad3H8(SOS)s 848 

Chloroplatinate, C«N'H»SK)*,2HCl,PtCT 349 

CarbamUdc, CWPH^O* « CWCyNH«»,H«08 349 

Solphocarbanilide, C»N«H»S» = CMCyNHW,H«S» 350 

MelaniUne, 0»N8H" = C»CyNAdH9,H3 .... .... .... 351 

PhoBphate.— Sulphate, C»N3H»*,HO,S03 .... .... 353 

Hydriodate. — Hydrobromate. — Hydrochlorate. — Hydrofluate. — 
Nitrate, C?«N»H«.HO,NO«.— Nitrate of Silver with Mdaniline, 

2C26N3H»,AgO,NO* ■•• .... .... .... .... 354 

Chloro-aurate.--C«N»H^,HCl,AuCl*.— Chloroplatinatc, 

C«WH»HCl,PtCl«.— Oxalate, (?WHW C^HH)^ .... 355 

Biniodomelaxiiline, (?3N»H"P = C^CyNAdPH^H^ 356 

Bibromomelaniline, C»N»H"Bi3 = C**CyNAdBraH7,H3 356 

BicUoromelaniline, 0«N»H"a« = C«CyNAdCl8H7,H» 357 

Binitromelaiimne, C»N»H"0« -- C^KJyNAdX'H^H* 358 

Cyaniline, C»N<H" = C«Cy8Ad«H8,H2 359 

Hydrobromate, C»N«HM2HBr.— Hydrochlorate, C»N^Hl^2HCl•-- 

Nitrate, C«N<H*,2HO,aN05 ..^ 361 

Chloro-aorate, C3^<HiS2HCl,2Ana*.— Ohloroplatinata, 

C»N<HW,2HCl,2PtCP.— Oxalate. 362 

Kcyanomdaniline, C»N»HW«!iC«Cy»Ad«H7,H« 362 

Chlorocyanilide, C»N»aH» = C»*Cy»Ad«H7,Ha 363 

OxaniUde, C»Nm»0* « C»(C<HO»)NAdH»,0» 364 

lielanozimide, C»N»H»0* = C«(C<HO«)CyNAdH«,0« 366 

SaccinaniUde, C»N»Hi«0< = C?*(C8H*09)NAdH»,0> 367 

Malanilide, C»N»H»«0« = C>*(C»H»0*)NAdH»,0" 368 

ItaoonaniUde, C«N»H»W = C«(CWH»02)NAdH»,0a 369 

Petttanitro-itaconanilide, C>«N7H"0» = C»*<CWH»0«)NAdX«0*,03 .... 369 

SulphophenaniUdc, C**NH"S»Q* 370 

Aio^nucleus C«N«H*. 

Diphanine, C^N^H* - C»N«H*,Ha 370 



CONTENTS. XIX 

Page 
Jzo-HMeliUi C^^ 

pmcyanogcDy CN' •••• t..t »*.* ••.• ••.• 371 

Appendix : Axolmic add .... .... .... .... 375 

Primary mucleui C^'H". 

(Jlly \jr*Dr •••• .•.• ***• *>•• •••■ •*!• O/D 

(kfygenHimelmu Ci*H>0>. 

fyiocatochiii or Ozyphenie add, C"HH>',0' 379 

Lead-aalt, C»H«Pb>04 382 

Comenic add, O^Kfi^ - C»HH>*,0« ..., .... 382 

Ammomiim.ialt, C»H>(NH^)Oi« .... ..., .... 384 

Potawram-ialts, C»H»K«0» and C»«H»KOW 385 

Sodinm^salt, CBH^aQi® .... .... .... .... 385 

Barium-aalta, C»H«BaK)w and C»m»BaOw 385 

Strontimn-salts, CinPSiX)i<^ and C^'SrOiA 386 

lime-aalta, C"BPCaK)«> and C"H»CaO>« 386 

Magnesivm.flalti, C»II3Mg>0«» and Ci>HSMgO» 386 

Lead-aalt, C>»IPPVOW 387 

Ferric salt, Pe«0»,2C»HK)io 387 

Cnpric salt, C^IPCuK)" .... .... .... .... „., 388 

SUver-salta, C»IPAg«0» and C»H»A«0«> 388 

Btbylocomcnic add, C»H80W - C4H«0»,CBH«08 389 

ChhriM'Wucleui OHSPlSiK 

Odoralbinf (P'Cl'H" .... •'•• .... .... »•«• 390 

aryeAlorJM-mHr^aitf CnK:iHH>«. 

CUorocomenio add, CbC1H»0» - CMaH»0*,0« 390 

Sa¥er-8alt8,C»ClHAg»0»andC"aH3A«Ow 391 

Ojgybromine'WHeleTu C°BrHH>^. 

Biomooomenic add, CMBrH«0>» - CMBrHW,0« 392 

SUTer-ialti, C»BrHAg*0» and C»BrH«AgO«> 392 

Oxyazo-nuekus C^H^O^. 

Comenamic add, C»NH»08 - CMNH»0»,0« 893 

Ammonium-salt, C»>NH<(NH<)P« .... .... ..., 394 

Barium-salts, C"NH»Ba«08 and CONH^BaO^ 33^ 

Comenamate of Ethyl, O^WO^ = C«H»0,C»NHHy 395 

Primary nueku* CH^. 

\/ll, \j MM .... •..* .... .... .... .... .... 395 

Valerol, C'*H'*',0' .... .... .... .... .... 396 



CONTENTS. 

Page 
Oxygen-nwletu C^^H^. 

Guiacic acid, C"H80« = C»2H»02,0* 397 

Oxygennucleiii C"HK)\ 

Pyrogallic acid. CWH«0« « C«li«0*,02 398 

Lead-BBlts, 6PbO,C»»H«0«; 2PbO,C»-II«0^aud 3PbO,2C«H«0« .... 401 

Aconiticacid, C»H«0«' =.C>2H604,03 402 

Aconitates, CKR'M'Os ; C^WM^O'^ and C^^1PM0>3 405—407 

Aconitate of Ethyl. C?*U}Hy^ = 3C^H»0,C»2H30» 408 

AcoDitanUic add, CP^NH'QS « CW(C'm»0*)NH*,0* 408 

AconitobUnil, C»N«H"08 = C«(C"H»0^)N^H»,OS 409 

0je}/gen.nucleu8 O'll*0\ 

Paracomenic acid, C»H^OW = C»2H^0«,0* 410 

Primary nuclftu C"H". 

Caproene, C^H^ .... .... .... .... .... 411 

Caproyl, C^H« or C2iH» .... .... .... .... .... 412 

Butyl-caproyl, C»Ha = (?H9,C»2H^3 .... 413 

MethyUcaproyli C"HW « C^H^C^H^^ 413 

Caproic alcohol - C>3H"02 = CJ2H>3,in02 413 

Caproic acid, Ci«HKO< = C^H»2,0* 414 

Caproates, C^H"MO* .... .... .... .... 416—418 

Caproate of Methyl. C'ni^O^ =« C«H>0,C"H"03 .... ... 418 

Caproatc of Ethyl, C«HiW « C*H«0,C»2H»0» 419 

Caproate of Amyl, (PRSiQi ^ cnV^O.OnV^O* 419 

Capronc, O^WH^ = C^tl'Kfi^OH)'^ 420 

Yaediucaoid .... .... .... .... .... .... 421 

Oxygen-nueUua C^H>K>, 

AnhydroM Caproic acid, C^H^K)' = C"H"0,03 421 

Oxygm-nucletu C"H'W. 

Pyroterebaic acid, C^By^ » CJSHiW.oa 422 

Adiplc add, C"H>W « C«HiW,0« 422 

Adipatea, CURt^M^O' 423 

Adipate of Ethyl, C»H»808 « 2Cm»0,CHH80« 424 

Oxygen-nucleus C'*HH)^, 

Terechrytic add, C"H80W == C>2HW,0« 424 

Lead-aalt, C"H«Pb«0« 425 

Amidogen-nucleui C^AdH"* 

LendD, C«NH»0^ - C»AdH",0* 425 

Uydrochlorate of Leadn, C>^Hi'0^,HCl .... .. 431 

Nitrolcudc add, CMNHiaoSHO,NO« .... ' .... "" .... 431 

Leucin with Oxide of Lead, PbO,C^H"0* and 9PbO,C'2NHiaoi 432 



CONTENTS. SXl 

Vnge 

Lendtf with Cupric Oxide, CnO,C>2NH»0< 432 

Leucin with Mercuric Oxide, HgO,C>2NH"0* .... .... 432 

OMyamidazo-nucleut C^AdH^O*. 

Amalic acid, C»2N*H«08 = Ci^NAdH^OSOS 433 

Primary nueleui C>*U". 

Oxygen-nucleui C^H^O*. 

Lactidc, CWHH)« = C»H80«,0» . 435 

Citric add, C»H»0" « C»«H*0«,08 436 

Hydrates, C^sH^OM + Aq. and + 2Aq 442 

Citrates of Ammonia, CWil*(NH«>W<; CJ2ir<NH<)«0" and 

C»H'(NH*)0" 445 

Citmtcs of Potash, C>2H*K»0"; C»2H«K20" and C^ITKO" 440 

Citrate of Potash and Ammonia, C»2H»(NH<)K»0" 446 

Citrates of Soda, Ci2H»Na»0"j C»H«Ni^O" and C^H^NaO" 447 

Citrate of Soda and Ammonia .... .... .... .... 448 

Citrate of Lithia .... .... .... .... .... 448 

Citrates of Baryta, C^H^BaaO" ; C^H^Ba^O" ; CMR^BaSO" and 

C^U'BaOM ? 448, 449 

Citrates of Strontia, C«H5Sr>0" and C«H«Sr80" .... 449, 450 

Citrates of Lime, C«H»CaH>" ; C^H^Ca^O" and C»H7CaO" 450, 451 

Citrates of Magnesia, C»«H«Mg»0" and C»H«Mg20" .... 451 
Cerons Citrates. — Citrates of Yttria, Gludna, Alumina, Thorina, 

Zirconium, and Vanadium .... .... .... .... 452 

Citrates of Chromium and Uranium .... .... .... 453 

Citrate of Manganese, C»2H«M»0" .... .... .... 453 

Potasdo-anthtfonic Citrate, C^H'K^Oi^C^IPSbO" .... 453 

Telluric Citrate ' .... .... .... .... .... .... 454 

Citrate of Zinc, CWH^Zn^O" and C«H»Zn50",C»H«Zn«0» 454 

Citrate 6f Cadmium .... .... .... .... .... 454 

Citrates of Lead 3Pb0,C»H»Ph»0"; 2PbO,CWH*Pb30»j 

PbO,C»H»Pb»OM ; C»H»Pb»OW; C"H«Pb«0" ; C«H«Pb-0" 

lmdCnH«Pb20" /. 455, 456 

Ammonio-citrate of Lead .... .... .... .... 456 

Perrons imd Ferric Citrates.»-Ammonio -ferric Citrate. — Sodio-ferric 

Citrate .... .... .... .... .... 457^ 458 

Citrate of Cobalt, CKH*Co»0" .... .... .... 458 

atrale of Nickel, C»H«Ni«0" 459 

Cupric Citrate, CuO,C»H«Cu»0" 459 

Mercnrous Citrate .... .... .... .... .... 459 

Ammonio-mereurous, Mercuric and Ammonio-mercuric Citrates 460 

Argentons Citrate, C"H<Ag<>Oi^ + Aq .... .... .... 461 

ArgcnUc Citrate, C"H»Ag»OW 461 

Citrate of Silver and Caldum, CaO.C'-HUgH^aO'* .... .... 461 

Citrate of Palladium .... .... .... .... .... 461 

Citrate of Aniline, Ci^H7,C»HB0i« 462 



xxii CONTBNTS. 

Page 
Comftiffaied Congxnmds qf CUrie acid. 

Tribasic Citrate of Methyl, C^B}*0^* - 3C9H»0,C»H*0" 462 

Bibatic Citrate of Methyl ? or Bimethylocitric acid ? C^H^^O^^ 

- 2C>HH),H0,C«H»0" 463 

Monomethylodtric acid, C^HSO,HO,Ci>H*OU .... .... .... 463 

Tribasic Citrate of Ethyl : Citric Ether, C»«H»0" - 3C<H»0,C»H»0" 463 

Citramide, C«N»H"08 .... .... .... ^.. .... 465 

CltraniUc acid, C»«NH"0"» = Ctt(C»H»0«)AdH^O• .... m.. 465 

Sflw-aalti: C»WHWAgOWandAgO,C"NH»AgO>» 466 

AnUine-aalt, C"Nir,C«xVH"OW. 467 

Citrobianil .... .... .... .... .... .... ••.• 467 

CiHobiaiiilic add, C»N«HWO» « C«(C»H«0«)Ad«H»,CH .... 468 

Barium-aalt, C*sN*HVBaOit». — Silver-ialt, C'N'Hi^AgOV. — 

Aniline-aalt, C"NH',C»»N«H»OW 469 

CttraniUde, C«N*H«0» « C»(C»HH>«)NAd*HM,0» 469 

Oryehlonne^nuelew, C»HbC1S0«. 

Ozychlorodtrio acid, C»H»CPO» -. C»H«a«0<,0« « 470 

OxyMudoffin'tmel€U9, C^AdH^O^. 

Lactamic acid, C»NH»W - C^AdHW,©* 471 

Ammoninm-salt, C^XdB\SH*)(^ 471 

Prinutry Nucleui C»H». J 

Oxygen-nucieui CH'W. 

Lactic add, C»H>^m « C»«H«0«,O» 472 

Lactates : Neutral C»HioiPO« ; — add C»»H"MO« 480 

Lactates of Ammonia, Potash a&d Soda ...• .... .... 481 

Lactate of Baryte, CWHWBi«)>« and C«H"BaO« 481 

Lactate of Stiontia, C«H»Sr»0» and C^ff^SrO" 482 

Lactate of Lime : Bibasic, Ci>Hi<<)a>0» 482 

Monobasic, Ci3H"CaOM .... .... ...• .... 484 

Chloride of caldum with Lactate of Lime, 

2CaCl,C"HMCa20» + 2Aq .... 484 

Lactote of Lime and Potash, C»HU>KCaO» .... .... 484 

Lactate of Lime and Soda, C^'H^ONaCaOi^ .... .... 485 

Lactate of Magnesia, C^B^'M^^ .... .... .... .... 485 

Lactates of Alumina, Chromium, Uraniam, C^H^{\J*C^H)^..^ 486 

Lactate of Manganese C^Uy^nH)^ .... .... .... .... 486 

Lactate of Bismuth, BiO',Ci<H»K>u 487 

Lactate of Zinc, C»H»^Zn«0» .... ^ .... 488 

Lactate of Zinc and Potassium, Ci'H^'^KZnO" .... .... 488^ 

Lactate of Zinc and Sodium, Ci*Hi<>NaZnO" .... .... 48» 

Lactate of Cadmium, C»«H»«Cd«0» 489- 

Stannous Lactote, 2SnO,C»HwSi«)« 489- 

Stannic Lactote '... .... .... .... .... 489 



CONTENTS. xxiii 

Page 

Lactates of Lead .... .... .... .... .... .... 489 

Ferroiu Lactate, C»H»FeK>» 490 

Forie Lactate 492 

Lactate of Cobalt, C«HMCo»OM 492 

Lactate of Nickel, CPnii0N?O» 492 

Cupric Lactate, 20uO,C»H»Cu«0» and C?*HWCuK)" .... 493 

Mercuroua Lactate, C^m}mf^O^ 494 

Mercuric Lactate, 2HgO.CKHWHg«0" 494 

Lactate of SUrer, C»HWAg«0" 495 

Lactate of Ethyl, C»H»0» « 2(C*H»0),CWHi«0» 496 

Lactate of Ethyl with Chloride of Calcium, CaCl,C»IP0O» .... 497 

Lactone? C»H»W 497 

Saroolactic acid .... .... .... .... .... .... 498 

Saicolactate of Lime, C^H^^CaSO^ .... .... .... 500 

Baroolactate of Zinc, (?*BPZjM^ .... .... .... .... 500 

Sarcolactate of Lead, C^H^Pb^O^ 500 

Saroolactates of Nickel and Copper .... .... .... .... 500 

Saicolactete of SUver, C^H'^^Ag^OB 501 

Anhyditraa Lactic add, C»H«0« - C»HM08,0» 501 

Primary Nucleus, C«H». 

Oxygen-mueleuM, C^«H»oO*o. 

Mocfe add, C«HJ^» - C»H»«Ow,0« 502 

Mucate of Ammonia, C>2H8(NH*)20i« and C»H»(NH<)OW .... 504 

Maeate of Potaah, C>»H8K«0m and CmH'KOW 505 

Mncato of Soda, C»H8Na«0W and C"H»NaO»« 506 

Mucate of Lithia — Macate of Baryta, C^»Ba?Oi« .... 506 

Mncate of Strontia— Mucate of Lime, C^^H^Ca^Qi^ .... .... 507 

Mucates of Magnesia and Alumina .... .... .... 507 

Potaado-chromic Mucate, KO,Cr80',C»«H80" .... .... 507 

Macate of Lead, 4FbO,C»H8PbK)w > and CaHspb^O" .... 508 

Ammoniacal Mucate of Lead .... .... .... .... 508 

Ferrous Mucate, CHsPe^O" .... .... .... .... 508 

Cupric Mucate, 20uO,C»3H8Cu8OW ? and C"H«Cu20w 508 

Mercnroua and Mercuric Mucates .... .... .... 509 

Mucate of SUver, O^H^Ag^O" .... .... .... .... 509 

Mucate of Methyl, C«H»*OW - 2C«H»0,C"H80" 609 

Mucate of Ethyl, C»H»OW - 2C*H»0,C»H80" 510 

Ethylomudc add, Ci«H"OW « C<H«0»,C»2H80" 511 

Paramudc add, C«H»W>,0« .... .... .... ... ... 512 

Sacdiaric add, C^W^^ - CKH^OW 0« 513 

Saccfaamtes, CMH«M«0W and C^H^MOW 516 

Saccharates of Ammonia, Potash, Soda, Baryta, Strontia and Lime, 

bibasic and monobasic .... .... .... .... 516 — 519 



XXIV CONTENTS, 

Page 

Chromic Saccharate — Saecharate of Bifmuth, C^>Bi^O>^' .^ 519 

Saocharate of Zinc, CWH^Zn^OW 619 

Saccharate of Cadmium, C»H«C<PO« 620 

SacchAratet of Lead .... .... .... .... .... 620 

Saccharatea of Iron, Copper and Mercury .... .... .... 622 

Saocharate of Silver, CUHSAg^O^* 422 

Oxyamidoffen-nucUui, C^Xd^R^^^, 

Mucamide, Ci«N»H«0« = C»Ad2HH)w O^ 523 

Appendix' to Mucic acid. 

Acid, C»H<CI»0» 523 

SllTcr-salt, C"H«Cl«Ag-"0« 624 

Chloropyromucyl, C><>H'C10' .... .... .... .... 624 

Azo-nueleu9, C»N«H80«. 

Baae obtained from Cratinine, C»N«H»oOS - C"N«H80«,1P 525 

Hydrocbloratc, 2C«N'^Hi»0«,3HCI + 3Aq 526 

Platinum-salt, 2C»N«HW08,3HCl,3PtCl2 + 6Aq 526 

Addenda to the Amy lene -series. 

Chloride of Valcryl, Ci"H30-Cl .... .... .... .... 527 

Bromide of Valcryl, C^'H'O^Br .... .... .... .... 527 

Trlbaaic Phosphate of Aroyl, 3Cwni50,PO« .... .... .... 627 



TEN-CARBON COMPOUNDS 

{Continued), 
AMYLENE SERIES. 



A. Primary Seriebi 
Primary Nucleus. Amylbkb, C'^H^^. 

Balard. (1844). y. Ann. Chim. Phys. 12, 320. 
Frankland* Ann, Pharm, 74, 41. 

Valerene (Kolbe) ; Myli (Oi]i.)--The amylene of Cahotin U howerer C^H^. 

Fcmuxtion and Preparation. 1. Potato fusel-oil is distilled with a 
rery concentrated aqneous solution (70° Bra.) of chloride of zinc in a 
retort, the ebullition taking place at about 180°; the resulting distillate, 
which is a mixture of C*^H»°, C»H» and C*»H*®, rectified, with change of 
receiver, the boiling point rising from 60° to 300°; and the portion which 
first passes over, shaken up with oil of vitriol, whereupon the pure 
amylene rises to the top when the liquid is left at rest, the higher com- 
pounds remaining dissolved in the oil of vitriol. (Balard.) — 2. Chloride 
of amyl, C^°H"C1, is distilled with the potash-lime. (Balard.) — 3. A strong 
glass tube, \ of an inch wide and 14 inches long, is filled to the depth of 
\\ inch with pasty zinc-amalgam, above which is placed a two-inch 
layer of granulated zinc (which likewise unites with the mercury, as the 
zinc in the amalgam is used up), and then 6 or 8 drachms of iodide of amyl; 
the tube drawn out at top to a very fine point; the air driven out oy 
heating the iodide of amyl to the boiling point ; the neck sealed; the tulie 
immersed in sand three inches deep, and heated for some hours to 
160° — 180°; and the point broken ofl* after the tube has cooled. Potas- 
sium, to the amount of 1 or 2 grammes, is then introduced; the tube 
again sealed, heated for an hour, and connected by means of a cork, after 
it has cooled and the point has been broken off, with a distillation-tube 
leading into a receiver surrounded with a freezing mixture; — then heated 
to 80° in the water-bath, whereupon f of the product passes over; and 
finally over the flame of a spirit-lamp, whereby the last third of the 

TOL. XI. B 



/>) 



2 AMTLENB : PRIMARY NUCLEUS C»Hio. 

distillate, consisting of C"H" [C»H»] is obtained. The first two- thirds 
of the distillate, which passes over at 80^, is a mixture of C^H' and C'H* 
[amylene C*^H" and hydride of amyl C*«H"]. This mixture contains 
84*2 p.c C and 15*9 H (excess O'l); it boils at the heat of the hand, and 
exhibits a vapour-density of 2*419; it has a pungent, rather unpleasant 
odour, somewhat like that of butylene; its taste is rather sweet at first, 
but afterwards unpleasant and tarry. Fuming oil of vitriol brought in 
contact with 100 vol. of the gas, condenses 46*78 vol. of it, consistmg of 
amylene-vapour, that is to say about one-half. (Frankland.) 

[There is no method given for obtaining amjlene in the free gtate from this mixture ; 
and Frankland appears to have deduced the properties of pure amylene merely from 
those of the mixture.] 

% 4. Sulphamylate of lime heated above 100° turns soft, blackens, and 
gives off a combustible gas mixed with a considerable quantity of 
sulphurous and carbonic acid. On passing this gas through milk of 
lime^ and collecting the remaining portion over water, a colourless, 
volatile combustible liquid collects on the surface of the water; and this, 
after washing with water and carbonate of soda, and drying over 
chloride of calcium, yields amylene. As the heat increases^ the quantity 
of amylene obtained diminishes, and a yellowish less volatile liquid is 
obtained, consisting partly of amylio ether (p. 7.) (Kekul^, Ann, 
Pharm. 75, 275.) IT 

Properties. Transparent, colourless, very thin liquid, having the 
odour of putrid cabbaee; boils at 39°. Vapour-density 2*68°. (Bfdard.) 
— Transparent, colourless liquid, boiling at about 35°; having a vapour- 
density of about 2*386; odour penetrating and disagreeable, recalling 
that of butylene. (Frankland.) — Boiling point 42 ; vapour-density 
2*43. (Kekul^.) It is used as an anaesthetic agent 













Balard. 




Kekul6. 


10 c 


60 


• ••■ 


85-71 


■ ••• 


8415 


•... o3*d 




10 H . 


10 


• •■• 


14-29 


• •■• 


14-70 


.... 14-7 .. 


.. 14*4 








CMflW . 


70 

C-vapour 

H-gas 


■ ••■ 


10000 


• ••• 

Vol. 
10 
10 


98-85 


.... 98-2 

Density. 
4-1600 








0-6930 






Amy leoe-vaponr. .. 




2 

1 




4*8530 








2-4265 





The vapour is rapidlv and completely absorbed by anhydrous sulphuric 
acid and by pentachloride of antimony. (Frankland.) 

[The most volatile portion of the oily mixture, which, according to 
Cahours, is deposited under strong pressure (x,411) from the illuminating 
gas obtained Irom resin, perhaps belongs to this head. This most volatile 
oil, T^ragarbure quadrihydrique of Couerbe, is, according to that chemist, 
colourless, does not solidify at — 15°, boils between 28 and 30°, and has 
a vapour-density of 2*00. The boiling point, calculated according to 
Gerhardt's law, is 30^ and therefore agrees with that of Couerbe's 
product better than with that of Balard*s; but the vapour-density of 
Couerbe's product differs considerably from that above calculated.] 



AMYL. 



IT. Amyl. 

C^oH" or C*>H« = goS" } 

Frakklajnd. Chem, Soc, Qu. J, 3, 30. Ann, Phai^. 74, 41. 
A. WuRTZ. iV. ^nn. CAm. Phys. 44, 275; iirm. PAa?-»*. 96, 367. 

Formation and Preparation. 1. By the action of zinc-amalgam on 
iodide of aro^l. The less volatile portion of the distillate thereby obtained 
consists chiefly of amyl (p. 1). This liquid was not acted upon by potassium. 
On rectifying it, the boiling point rose rapidly to 155^ at which point it remained 
stationary till nearly the whole had passed over. The liquid which distilled at that 
tt^mperature was collected apart. (Frankland.)— 2. By the action of Sodium on 
iodide of amyl. No decomposition takes place in the cold, but, on the 
application of heat, the sodinm acts upon the iodide of amyl in the same 
manner as upon iodide of butyl (x, 563). The liquid separated from 
the resulting iodide of sodium by distillation in the oil-bath is rectified, 
the portion which passes over at 158® being collected apart. (Wurtz.) 
— 3. By the electrolysis of caproic acid : 

. C»2H«o* « C«>H" + 2C0» + H. 

A concentrated solution of caproate of potajsh is subjected to the action of 
a zinc-carbon battery of six elements in the apparatus used by Kolbe 
for the electrolysis of acetate of potash (vii, 247). The liquid soon 
becomes turbid, and oily drops collect on the surface. This oil is removed 
by a pipette, and distilled with an alcoholic solution of potash, then 
washed with water, dried, and rectified. The product thus obtained Is amyl. 
The potash retained caproic [?] acid. (Brazier and Gossleth, Ghem, Soe, Qu. J. 
3, 222.) 

Properties. Transparent, colourless liquid haying a slight ethereal 
odour and a burning taste. (Frankland.) Colourless, mobile liquid 
having an aromatic odour. Turns the plane of polarisation to the right; 
but preparations obtained with iodide of amyl produced from different 
samples of amylic alcohol possess this power in different degrees. 
(Wurtz.) Sp. gr. = 07704 at 1^ (Frankland); 07413 at 0°, and 
07282 at 20 . (Wurtz.) At Z(f it becomes thick and oily, but does not 
solidify. (Frankland). — Boils at 155° under a pressure of 728mm. 
^Frankland); at 158° (Wurtz); at 155°. (Brazier and Oossleth.) Vapour- 
density = 4 90 (Frankland); 4*956. (Wurtz). 



10 c 

11 H 


60 
11 


• ••# 

* • ■ ■ 


Frankland. 

84-5 .... 84-3 

15-5 .... 15-3 


Wurtz. 

84-20 

15-65 


Braz. & Goss. 
.... 84-26 
.... 15-70 






C«»H" 

C-vapour 

H.gas 


71 


Vol. 
10 
11 


1000 .... 99-6 

Density. Or : 
.... 4-1600 
.... 0-7623 


. 99-85 

Vol. 
20 .... 
22 .... 


.... 99*96 

Density. 
8-3200 
1-5246 


Amyl-vapour 

• 


•••• •••• 


1 


.... 4-9223 




9-8446 
4*9223 



For the controversy about the formule and vapour-volumes of the alcohol-radicals, 
see yi\, 172 ; the double formulK, e. y. C^H^ for amyl, are powerfully corroborated by 
Wortx's discovery of the compound radicals, ethylo-butyl, eUiylo-amyl, &c. (p. 5.) 

B 2 



4 AMYLENE: PRIMARY NUCLEUS C^H^. 

Decompositions, 1. Amyl does not take fire in tbe air at ordinary 
temperatures, bat on being heated, its vapour bums with a white 
smoky flame. (Frankland.) — 2. It is not affected by fumiug sulphuric 
acid, and is but very slowly oxidised by boiling faming nitric acid, or 
by a mixture of nitric and sulphuric acid, the liquid acquiring the odour 
of valerianic acid. (Frankland.) Strong nitric acid dissolves amyl when 
boiled with it for some time, the vapours being continually condensed 
and allowed to flow back again; and the solution, when neutralised with 
carbonate of potash and conceotrated, yields a neutral yellow substance 
sparingly soluble in water, and ultimately solidifies to a crystalline mass 
of nitrate of potash, which, when treated with alcoholic potash, yields a 
small quantity of a yellow deliquescent potash-salt; no valerianic acid 
could be detected among the products of the oxidation. (Wnrtz.) — Amyl 
does not dissolve in oil of vitriol or in fuming sulphuric acid; when left 
for some time in contact with the latter, it blackens and ultimately gives 
off sulphurous acid. When the vapour of anhydrous sulphuric acid is 
passed into amyl cooled by a freezing mixture, the liquid slowly blackens, 
and gives off sulphurous acid: but no conjugated sulphuric acid is 
produced. — S. Hydriodic and hydrochloric acid do not act upon amyl 
even at 300°. — 4. Pentachloride of phosphorus does not act upon amyl at 
ordinary temperatures; on the application of heat, it dissolves and sepa- 
rates out with scarcely any alteration on cooling; after long boiling, 
however, the amyl is decomposed, with evolution of hydrochloric acid 
and terchloride of phosphorus, and fonnation of substitution-products. 
When 7 pts. (1 At.) amyl were boiled with 21 pts. (2 At.) pentachloride 
of phosphorus, till the liquid began to show colour, the residue then 
washed with water, dried over chloride of calcium and distilled, the 
thermometer quickly rose to 210°; between 210° and 215° a distillate 
passed over containing 58*26 p. c. C and 10*61 H; and between 215° and 
220°, another distillate containing 57*04 p. c. and 9*80 H, agreeing nearly 
with the formula C»^H>«Cl or C»H*»Cl« which requires 56 920 and 9 48 H. 
Equation for the formation of this product : 

CWHU + PC15 « C'0H»C1 + PCP + HCK 

When 5 pts. of amy] were boiled for several days with 30 pts. of the 
pentachloride (1 At. to 4 At.), the loss volatile vapours being condensed 
and made to flow back, the pentachloride of phosphorus gradually disap- 
peared, with formation of hydrochloric acid and terchloride of phosphorus; 
as soon as tbe liquid began to show colour, the boiling was stopped, and 
the product wasned, dried and distilled. Tbe distillate obtained above 
270°, was a colourless neutral liquid, heavier than water, insoluble in 
water, but soluble in alcohol; it contained 4180 p c. C and 6*86 H, 
agreeing nearly with the formula C*°H*C1' or C*H*®C1* which requires 
48*25 C and 6 42 H. When this liquid was heated in a sealed tube with 
alcoholic potash, it yielded chlori<le of potassium, and, after addition of 
waier, an oily liquid separated out, which distilled at about 220^, but 
without exhibiting a constant boiling point. (Wurtz.) — 5. Pentachloride of 
antimony acts upon amyl with evolution of hydrochloric acid and forma- 
tion of substitution proaucts. — 6. Chloride of mercury heated with amyl 
is reduced at about 250°, with evolution of hydrochloric acid; but no 
chloride of amyl is formed. (Wnrtz ) 

Combinations, Amyl unites, though not directly, with oxygen, 
chlorine, iodine, &c.. forming a series of compounds homologous with 



HYDRIDE OF AMYL. 5 

the ethyl-compounds. Also with hydrogen, with rarioits metals, e,g, 
zinc, tin, <fcc., and with other organic radicals, such as ethyl and butyl. 
It is insoluble in water, but mixes in all proportions with alcohol and 
ether. (Frankland.) 

Ethamyl. C"H"=QMtJu \ — Preparaiion, 70grm. iodide of amyl 

and 60 grm. iodide of ethyl were decomposed with sodium; and in 
another operation, 84 grm. iodide of amyl and 27 grm. iodide of 
ethyl with 8 grm. of sodium. When the action was nearly at an end, 
50 grm. iodide of amyl> 40 grm. iodide of ethyl, and 12 grm. sodium 
were added to the product, and -the heating continued ; altogether 1 54 
grm. iodide of amyl and 127 grm. iodide of ethyl were decomposed 
with 34 grm. sodium; but these materials were divided as above, in 
order that the action might not become too violent. When the decom- 
position was ended, the product was distilled in the oil-bath, the portion 
which went over below 1.20*' being collected apart, and this distillate was 
heated under a sealed glass tube wi^h excess of sodium, to complete the 
decomposition of any organic iodine-compounds that might still bo 
present. The liauid was then again distilled ; and the distillate sub- 
mitted to repeated fractional rectifi(»tion, yielded ethamyl in the form of 
a liquid which passed over between 87^5 and 89*5, and for the most 
part at 88"^. 

Ethamyl has a sp. gr. of 0^06;9 at 0°; boils at 88^ Vapour-density 
3*523. It turns the plane of polarization to the right. It is but slightly 
attacked by pentachloride of phosphorus at its boiling point (88°); but 
when the two substances are hoated together in a sealed glass tube above 
100°, a more violent action takes place; the products could not however 
be examined because the tube exploded. (Wurtz, AnVi, Pharm, 95, 370.) 

Wnrti. 

14 C 84 .... 84 84-02 

16 H 16 .... 16 16-14 

C"H>« 100 .... 100 100-16 

Vol. Density. 

C-vapoi^r 14 .... 5-8240 

H-gas 16 .... 1-1088 

Vapour of Ethamyl 2 .... 6*9328 

I .... 3*4664 

08119 ] 

BtOamyl, C**H~=riioiju \ — 160grms. of a mixture of iodide of 

butyl and iodide of i^myl were decompose4 by 20 grm, sodium. On 
distilling the product, the greater portion passed over between 130^ and 
140^; and by repeated fractional distillation, the butamyl was obtained 
in the form of a lic^uid which had a sp.gr. of Q-7247 at 0% boiled at 132^, 
and exhibited a vapour-density = 4*465. (Wurtz.) 

Wurtz, 

38 C 108 .... 84-37 94-38 

20 H 20 .... 15-63 15^77 

CWH» \Z% .... 100-00 10015 '' ' 

Vol. Density, 

C-vapour 18 .... 7*4880 

H-gas 20 .... 1-3860 

Yap. of BuUmyl \, 2 ' .... 8*8740 

1 .... 4*4370 If. 



AMYLBNE: PRIMARY NUCLEUS Om^. 



Hydride of Amyl. 

C»*H» = C"H^H» = C"H",H. 

Fbankland (1850). Ann, Fharm. 74, 41. 

Amyl'kydroffen, Amyl-wat$er9ioff'f Xtfmy/tf. — Constitutes, perliapSf the nost 
volatile portion of enpione, and probably exists also in ooal-gas. 

Formation and Preparation, 1. The mixtnre of amy] and hydride of 
amyl (p. 2) which distils orer at 80° is placed in contact at— 10°, 
for seyeral honrs, with oil of vitriol saturated with anhydrous salphuric 
acid, and frequently agitated, whereupon a stratum of liquid rises to the 
surface ahout eqnsu in volume to the mixtnre employed. The product is 
then distilled in the water-hath at a gentle heat, whereupon the hydride 
of amyl passes over, whilst the npper liqnid is reduced to a lajrer half 
as deep, and consisting probahlv of a conjugated compound of amylene 
with sulphuric acid; lastly, the distillate is freed from admixed sul* 
phurous acid hy contact with sticks of fused hydrate of potash. — 2. More 
conveniently: Iodide of amyl is heated with water and with zinc to 
142° in a long glass tube drawn out to a point at the open end; the 
mixture left to cool after the action is completed ; the point of the tube 
broken off; the open end connected by means of a cork with a distil- 
lation-tube; and the liquid distilled at 60°, the distillate placed for 24 
hours in contact with hydrate of potash, and rectified in the water-bath 
at 35°. 

Properties. Transparent, colourless, very mobile liquid, which does 
not solidify at 24°; has a density of 0-6385 at 14°; boils at 30° when 
the barometer stands at 0*758 met. and exhibits a vapour-density of 
2*4657 to 2*4998. Has a pleasant odour like that of chloroform. 

Frankland. 

10 C 60 .... 83-33 .... 83-33 

12 H 12 .... 16-67 .... 16-62 

C'm» 72 .... 10000 .... 99-95 

Vol. Densitj. 

C-vapour 10 .... 4-1600 

H-gas 12 .... 0-8316 

Vap.ofCWH* 2 .... 4-9916 

1 .... 2-4968 

[That this compound is C^W^, and not as supposed by Frankland, CH*, follows 
rom its vapour-density, and from its boiling-point ; the latter is indeed higher than it 
should be for C*^H^, according to Gerhardt's law. {n\, 67.) Similar obserrations apply 
to the oomponnd described by Frankland and Kolbe (Ann, Pharm, 65, 270), as 
methyl* CH*, which should really be regarded as C^H*, and stands to ethylene C*H^, in 
the same relation as marsh-gas CH^ to methylene CH^ ; similarly for the compound 
described by the same chemists as ethyl, C^H*, which should be regarded as C"H>®; also 
.the valyl of Kolbe, C^H*, in which, for similar reasons, the atomic weight should be 
doubled, so that the so-called radicals are actuaUy compounds of a nucleus with 2 At. 
H. — Compare vii. 172.] 

Decompositions, Hydride of amyl bums with a white, very luminous 
flame. It is but slowly attacked by the strongest oxidising agents, and 
by fuming oil of vitriol not at all. 

Combinations. It is insoluble in water. It dissolves readily in alcohol 
and ethery bcinfl: separated from the former by water. (Frankland.) IT. 



M£THAMTUC BTHBR. 



Oxide of AmyV or Amylic Ether. 

Balard. rL844.) N. Ann. Chim, Phys. \2, 299. 
Amyloxyd, Sfylaiher, Ether amyligue. 

Formation and Preparation, Chloride of amyl mixed with alcoholic 
potash in a strong sealed tabe and heated to 100°, yields amy lie ether 
and a deposit of chloride of potassinm. (Balard.) This prodact was most pro. 
bably Tiiiamylie ether, (p. 8.) — Gaultior {Compt, rend. 15,171) states that 
by distilling fusel-oil with oil of vitriol, he obtained amyltc ether, among 
other prodacts, as a coloarless, agreeably smelling liquid, which dissolved 
with red colour in oil of vitriol, bat boiled at 170 [certainly too higli 
for amylic ether]. A similar liquid was obtained in the same manner 
by Rleckher. See alto WiUismson (p. 8). 

Properties. Colonrless liqnid boiling at lll^to ]]2° and having an 
agreeable odour. (Balard.) 

IOC 

11 H 

O 







Williamson. 


60 


... 75-^5 . 


75-81 


11 


13-92 . 


14-09 


8 


... 1013 . 


10-10 



C»H»0 79 100-00 100-00 

Decompomtion. The ether prepared by Balard's method is converted, 
when treated with chlorine-gas nuder the influence of heat and sunshine, 
till the chlorine no longer appears to act, into a product which may be 
regarded as a mixture of bi-, quinti-, and sexti-chlorinated amylic ether 
with chloraldehyde and seequichloride of carbon. For : 

2CWC1»0 + 6C1 - C<C1*0« + 4C*Cl«. 

The product gives up to water, terchloracetic acid produced from the 
chloraldehyde (ix, 209); the rest of the product, heated with alcoholic 
potash deposits a large quantity of chloride of potassium, and after- 
wards, on dilution with water, a brown^ neutral, oily, chlorinated mixture 
of several substances, while valerate, terchloro valerate and quadrichloro- 
valerate of potash remain dissolved. The bichlorinated amylic ether 
acted upon by potash, yields in fact valerate of potaah : 

C»CPH»0 + 3KO - CWH'KCH + 2KC1 ; 

the quintichlorinated ether yields terchlorovalerate of potash : 

C»«CI»H«0 + 3K0 - C»«a«tt«KO< + 2KC1; 
and the sextichlerinated ether yiekls qnadrichlorovalemte of potash: 

CWC1«H»0 + 3KO =. CJ^Cl^H'KO* + 2KC1. 

The dark colour of the separated neutral oil is due to the brown sub- 
stance produced by the action of the excess of potash on the chlorova- 
lonanic acid, (M«.lafiruti, N. Ann. Chim. Phys. 27, 417.) 



8 AMYLENE : PRIMARY NUCLEUS C^R^. 



% Methamylic Ether. 

C«H^*0* = C*HH),C^«H"0 = ^oh'u } 0\ 
A. W. Williamson. Chem. Soc. Qu. J. i, 108, 234. 

Methylaie of Amylf Amylatt qf MeihyL 

FoTm/aUm and PreparcUian. 1. By the action of iodide of methjl 
on amjlate of sodium G^'H^^KO^ or of iodide of amy] on metbjlate of 
sodium, C»H>KO», 

C»H"KO« + C«H«I 1 „ KI 4. CWHiW 
Or : C?H»KO» + C»H"I / = «^A + ^ « '^ 

It is purified in the same manner as vinon^ethylio ether (yiii, 193). — . 
2. By the action of oil of vitriol on a mixture of 1 At. methjlio and 1 At. 
amyUc alcohol, the process heing condmstod as in the continuous method 
of preparing common ether (viii, 173). The product is a mixture of meth- 
amylic ether with methylic ether, amylic ether, and excess of the two 
alcohols, which may he removed by distillation over hydrate of potash. 
The methamylic ether is then purified by fractional distillation, which 
is easily effected, in consequence of ^he great difference of the boiling 
points of the three ethers. 

Properties. Transparent, colourless liquid, which boils at 92^, and 
has a Taponr-density of 3*74* 

WilliamspD. 

12 C 72 .... 70-59 70-24 

14 H 14 .... 13-72 13-87 

2 O 16 .... 15-69 15-89 

C»H"0* 102 .... 100-00 100-00 

Vol. Density, 

C-Taponr 12 .... 4-9920 

H-gag 14 .... 0-9702 

0-gaa 1 .... 1-1093 

^^" Vap; of C»H»H)» 2 .... 70716 ' 

1 .... 3'53§7 

The ether analyMd was prepared by the first proo^, 



% Vinamylic Ether* 

C»W«0» = C*H»0,C"H"0 = ^oH" } 0* 

WiLLiAMBOir. Chem. Soc, Qu. J. 4, 108, 234. 

Formation and Preparation. Exactly similar to that of methamylic 
ether. 



AMYLIC ALCOHOL. 9 

Prapertiei. Tiunsparent^ colourless liquid, boiling at 112°. Vapour- 
densitj 4*042. 

WiUiamsOD. 
a. 6. 

14 C 84 .... 72-41 .... 72-42 .... 7246 

16 H 16 .... 13-79 .... 13-99 .... 13-73 

2 16 .... 13-80 ... 13 59 .... 1381 

C"H»«0* 116 .... 100-00 .... 100,00 .... 10000 

Vol. Densitf. 

C-vapour 14 .... 5-8240 

H-gM 16 .... 1-1088 

O-gas 1 .... 1*1093 



■■» ^ 



Vap.ofC"H^W 2 .... 80421 

1 ... 40210 

a was preparod by the action of iodide of ethyl on amylic alcohol ; b, by the actioa 
of oil of vitriol on a mixtore of vinic and amylic alcohols. 

The product which Balard obtained by the action of alcoholic potash on chloride of 
amy], and supposed to be amylic ether, was probably rinamylic ether. (Williamson.) 7. 



Amylic Alcohol. 

CioHiK)* = C^^^H^^ H»0*. 

Gabriel Pelletan. J. Ghim, med. 1, 76; also Ann, Chim, Phys, 30, 

221; alsoiV. pr. 1, 135. 
Dumas. Ann. Chim. Phys, 56, 314; also J. Chim, med, 10, 705; also 

Pogg. 34, 335; also Ann. Pharm. 13, 80; also J, pr, Ohem, 3, 321. 
Dumas & Stas. Ann. Chim. Phys. 73, 128; also Ann. Pharm, 35, 143; 

also J, pr, Chem, 21, 278. 
Cahoubs. Ann. Chim. Phys. 70, 81; also Ann Pharm. 30, 288; also 

J, pr. Chem. 17, 213. — Ann. Chim. Phys. 75, 193; also Ann. Pharm. 

37, 164; also J. pr. Chem. 22, 171. 
Apjohn. Phil. Mag. J, 17, 86. 
Balard. N. Ann. Chim. Phys. 12, 294; also J, pr. Chem. 34, 123; 

abstr. Compt, rend. 19, 634; abstr. Ann. Pharm. 42, 311. 
RiBCKHER. Jahrb. pr. Pharm. 14, 1. 
Pasteur. Compt. rend. 41, 296; Ann. Pharm. 96, 255; Chem. Soc. 

Qu. J. 8, 277. 

AmylalkoMt Hydrated Oxide qf Amyl, Hydrate of Amyl, Potato F^ueUoif^ 
Com Fueel'OU: MyUUkohol, Kartoffet^eVU, Putelol, Amytal, Amy loxyd»hy drat, HmUe 
de pomme de terre, Hydrate d^Oxyde d'Amyle, Aleool amylique. ^^ Knomn since 
Scheele (Crelt. Ann. 1785, I, 61); more exactly investigated chiefly by Pelletan, 
Dumas, Cahours, and Balard. 

Sources. In brandy from potatoes, barley, rye, beet-molasses, grape- 
husks and wine lees, often mixed with margaric acid and (Bnantnic 
ether. Fnsel-oil is contained, not only in ordinary potato-brandy, but 
also, according to Dubrunfaut, in that which is obtained by converting 
potato-starch into grape-sugar by means of sulphuric acid, and fermenting 
the sugar. Barley-brandy yields by rectification, nothing but potato 
fusel-oil, without any of the substances which Mulder & Kolbe (vid. inf.) 



10 AMYLENE: PRIMARY NUCLEUS O^H^. 

foand in rye-brandy. (Medlock, Ann. Pkarm. 69, 214.) — Wort prepared 
from malt which has been roasted with peat-smoke^ as it is done in 
Scotland, yields, when made to under^ the vinous fermentation and 
distilled, a spirit (whisky) which contains fusel-oil. Wort from nnmalted 
barley yields, after fermentation, a spirit much richer in fnsel-oil. Bat 
if the wort, before fermentation, be boiled with hops, the spirit obtained 
from it is free from fusel-oil. (61asi?ford, Ann. Pharm. 54, 104.) ^^ In 
the rectification of brandy prepared from rye, thedistillnte obtained after 
the greater part of the alcohol has passed over, is turbid and contains 
fusel-oil. This distillate when cooled deposits a tallowy substance, of the 
nature of fusel-oil. (Scheele. Opusc. 2,275.) It deposits on the flannel in the 
funnel of the receiver, a salve-like substance havinff the odour of fusel- 
oil. (Qehlen, ScJiw. ], 277.) The milky liquid, which, in the rectification 
of corn-brandy, passes over after the alcohol, leaves when filtered, a soft 
solid mass coloured green by oxide of copper, and from which, even at 
ordinary temperatnros, delicate white needles sublime in the vessels in 
which it is kept. (Gm ) This substance, which was more particularly 
examined by Gehlin, was designated by the anthor (ffandbuch, Aufl. 3, 
ii, 421) as fiud-camphor. But, according to recent investigations, it is 
a mixture of potato fusel-oil with margaric acid, (Buanthic ether or 
(Bnanthic acid, and corn-oil. According to Kolbe {Ann. Fharm. 41, 53), 
the dark brown, greasy mass, smelling strongly of fusel-oil, which 
collects in the receiver during the distillation of corn-brandy, contains, 
besides fusel-oil, a very large quantity of margaric acid, a small qnan- 
tity of oenanthic acid, and from 1 to 2 p. c. of corn-oil. Mulder {Pogg. 
41, 582) found, in a dark brown, disagreeably smelling oil obtained in 
the rectification of corn-brandy, which had a greenish yellow colour after 
rectification, nothing but osnanthic ether, and the substance which he 
calls corn-oily Oleum siticum, which is greenish yellow and smells like 
Phellandrium. [Since, however, it was obtained by distilling the entire 
oil with potash-ley, whereupon oenanthate of potash remained and alcohol 
passed over with the corn-oil, and since the corn-oil which Mulder obtained 
with dilute potash was = C^H"0*, while that which was obtained with 
concentrated potash = C^H^'^O, it appears that all kinds of decompo- 
sition-products were formedj. Mulder afterwards found {Ann. Pkarm. 
45, 67; also J. pr. Chem. 32, 219), in some kinds of corn fosel-oil, 
a large quantity of margaric acid, but in others a small quantity, and 
in others again, none at all. Medlock {^Ann. PJiarm. 61^, 214) obtained 
by the rectification of rye-brandy, nothing but potato fusel-oil. 
A volatile oil from corn-brandy is described by Buchner. {Repert, 24, 270.) 
The brandy obtained from beet-molasses which has undergone the vinous 
fermentation, yields an oil, which after sufficient purification, affrees 
perfectly with potato fusel-oil. (Gaultier de Claubry, Compt. rend. 15, 
171; also Ann. Pharm. 44, 127; also J. pr. Chem. 27, 56.) In the recti- 
fication of brandy obtained from grape-skins after the wine has been 
expressed ( Weintresterbranntwein), there passes over, after the pure 
alcohol, a spirit containing fusel-oil, and afterwards a watery liquid 
turbid from the presence of oil. On mixing these last two distillates 
together, adding water, and leaving the mixture at rest, the wtae fosel- 
oil rises to the surface, in the form of a thin colourless liquid which soon 
acquires a yellowish tint, cannot be distilled withont decompositioii, baa 
n pungent odu.ur, and intolerably sharp taste; a single drop oi this liquid 
is sufficient to impart a disagreeable flavour to a litre of alcohol. (Amber- 
gier, Ann. Chim. Phys. 14, 210.) This wine fusel-oil is a mixture ti a 



AMYLIC ALCOHOL. 11 

lar^ quantity of oananthio etber with potato fusel-oil and a little alcohol; 
and it is chiefly the oonanthic ether contained in it^ which imparts to the 
alcohol the disagreeable taste of grape-skin brandy. (Balard, iV. Ann, 
Oiim. Phys, 12, 294 and 327.) The wine fusel-oil obtained by the 
distillation of Jena wine-lees is thickish; deposits at— 4°, a larse quantity 
of camphor-like matter; has a density of 0*856; is yellowish brown, but 
soon becomes dark brown; has a not very unpleasant odour, but an 
excessively repulsive taste, and excites a persistent and violent irritation 
in the mouth and throat; in the fresh state it does not redden litmus, but 
after keeping for a year, reddens it strongly. The spots which it makes 
upon paper do not disappear till they have been heated for some time. 
It bnms with a dark yellowish red flame, and acquires a dark carmine 
colour by contact with oil of vitriol, &e, (Stickel, y, Br, Arch. 9, 22; 
compare also Buchner, Heperi. 58, 86.) 

It is highly probable that fusel-oil does not exist ready formed in 
potatoes, com, grapes, &c. but is produced by fermentation. — Pay en 
supposes the fusel-oil to pre-exist in potatoes, because he was able to 
extract an oil from potato-starch by treating it with alcohol, and because, 
in converting potato-starch into sugar by ooiling it in a still with water 
containing sulphuric acid, he obtained an oil smelling of starch, and 
amounting to 0*001 of the starch; this oil was however more volatile 
than fusel-oil. But, according to Bucholz, the oil extracted by alcohol 
from potatoes, is buttery, and without the taste or smell of fusel- oil; 
similar observations apply to that which is obtained from rye. Schrader 
and Korte {Schw. 1, 273) suppose that the fusel-oil is produced from fatty 
matter of this kind, when the fermentation is badly conducted and the 
product too quickly distilled. According to Liebig's suggestion {Chem, 
Biiefey 165), fusel-oil is produced by partial decomposition of common 
alcohol : 

5C<H«0a - 2C>0H»W + 6HO j 

and, according to Dumas & Balard, by a decomposition of grape-sugar 
induced by excess of ferment [according to what equation 11. — IT Chancel 
{Compt rend. 37, 410,) supposes that amylic and propylic alcohol are 
produced together by the decomposition of grape sugar, according to the 
equation : 

2CWH»0W « C«H802 + C'«H»W + 8C0» + 4H0 ; 

{vid. ix, 399); but propylic alcohol does not appear to be alw^s con- 
tained in fnsel-oil (comp, Wnrt«, Ann, PJiarm, 93, 110) ^. Finally, 
according to the supposition of Deschamps {N, Ann, Chim. Phys. 12, 
383), wine fnsel-oil is produced only from the skins of the grapes by 
fermentation and subsequent heating to 100°. 

Preparation. In the rectification of potato or com brandy^ the fusel- 
oil being less volatile remains behind for the most part, passing over 
in considerable quantity, together with water, only with the last portions 
of the spirit, and separating out on the surface of the liquid when a 
larger quantity of water is added. Crude fnsel-oil, which may be obtained 
in abundance from the large brandy distilleries, is yellow, reddish yellow 
or red-brown, of sp. gr. 0-84 to 0*93, and still retains alcohol and water. 
It is freed from alcohol by washing with water, and then from water by 
rectification over chloride of calcium. (Pelletan.) A small quantity of alcohol 
remains with it. (Dnmas). — The oil is sKaken up with an equal quantity of 
water; then distilled after being separated from the water by treating 



12 AMYLENB: PRIMARY NUCLEUS Om^. 

with au equal quantity of pounded chloride of calcium; the receiver 
changed as soon as the boiling point reaches 131°, at which point it 
remains steady till the end of the distillation; and the latter distillate 
rectified, rejecting the portion which goes over last. The fusel-oil 
obtained below 131° still retains alcohol. (Apjohn, Phil. Map. 17, 86.) — 
The oil freed from the greater part of the alcohol by repeated agitation 
with water, is rectified; the receiver changed as soon as the boiling 
point rises to 132°, at which point it then remains constant during the 
whole distillation; and this distillate repeatedly rectified. (Cahours.) — 
A similar process is followed by Kopp {Ann. Pliarm. 55, 196), according 
to whom, however, the boiling point slowly rises above 1 32°; he examined 
the liquid which passed over at 134°. — According to Krutzsche (</. pr, 
Chem, 31, 1,) the boiling point of the crude oil washed with water, 
remains stationary for some time at 132°, and then gradually rises above 
160° [probably n*om admixture of marj?aric acid or oBuanthic ether]. 
But the distillate obtained between 132 and 135°, yields after repeated 
rectification an oil boiling at 132°. — The crude oil is distilled without 
any preparatory treatment, whereupon a mixture of oil, water, and 
common alcohol passes over; and the portion which distils over between 
130° and 132°, is purified by repeated rectification. (Dumas, Medlock, 
Rieckher.) 

2. To obtain pure fusel-oil from the oil of grape-skin brandy, this 
oil is distilled; the portion which goes over between 130° and 140° 
collected apart, and re-distilled after addition of hydrate of potash, 
whereby the admixed oenanthic ether is decomposed and the oenanthio 
acid retained; and the receiver changed, as soon as the boiling point 
has risen to 132°: the fuseUoil thus obtained is very pure. (Balard.) 

IT Active and Inactive Amylic Alcohol. — The fusel-oil of commerce 
consists chiefly of a mixture of two kinds of amylic alcohol,— one active, 
and the other inactive with regard to polarised light. These two varieties 
are exactly similar in their chemical properties; difler but slightly in 
density and boiling point; and give rise, under similar circumstances, to 
products which resemble each other in all respects, excepting in their 
relation to polarised light, those which are derived from the active 
alcohol being themselves active, and those which result from the inactive 
alcohol being themselves also inactive. — The proportion of the active and 
inactive alcohols in fusel-oil varies according to its origin; thus the fusel-oil 
obtained by fermentation of the juice of mangold-wurzel contains about 
<me-third of active, and two-thirds of inactive amylic alcohol, whereas 
that which is produced by fermentation of the molasses contains about 
equal parts of the active and inactive alcohols. The two alcohols cannot 
be separated by fractional distillation, but only by fractional crystallisa- 
tion of the active and inactive sulphamylates of baryta. For this purpose 
it is necessary to prepare a large ouantity of sulphamylate of baryta 
from crude amylic alcohol rectified by a single distillation, in order to 
free it from water and vinic alcohol. The amylic alcohol thus far purified 
is mixed, as usual, with an equal weight of sulphuric acid, the mixture 
treated with carbonate of baryta, then filtered and left to crystallise. 
The crystals have all the same aspect, lustre, form, and angles; and, as 
in the case of a perfectly constant and homogeneous substance, the salt 
may be crystallised either wholly or partially any number of times, 
without the slightest change in the 'aspect of the crystals. Neverthe- 
less the mass is really composed of two kinds of crystals differing in 



AMYLIC ALCOHOL. 13 

solttbilitj, and in their action on polarised light, -^^-one being, indeed, 
actiire, and the other inactive. They are very difficult to separate, in 
consequence of their complete isomorphism. Nevertheless, the active 
salt is 2^ times more soluble than the inactive; and if the first crystals 
which separate be recrystallised about 20 times, a product is at length 
obtained which has no action on polarised light; and by repeatedly 
crystallising the mother-liquor, a solution is ultimately left containing 
nothing but the active salt. Lastly, on extracting from these two varieties 
of the sulphamylate, the amylic alcohol of which they contain the 
elements, it is found that the more soluble salt yields an amylic alcohol 
which rotates the plane of polarisation to the left, and to the amount of 
20° in a tube 50 centimetres long, while the less soluble salt yields an 
amylic alcohol which has no perceptible action on polarised light. 
(Pasteur, Ckmpt. rend, 41, 296) %. 

Properties. Transparent, colourless, thin oily liquid, greasy to the 
touch. (Pelletan.; Solidifies at — 19° to — 20^ forming a crystalline, 
laminated mass, and melts again at — 18^ (Pelletan.) Does not solidify 
at — 21° (Apjohn); requires for its solidification a temperature of — 23° 
or still lower. (Pierre.) Sp. gr. : 0-82705 at 0° (Pierre, N. Ann, Chim. 
Phys. 19, 197); 08253 at 0° and 08137 at 15° (Kopp); or, according to 
a later determination by Kopp, {Ann Pharm. 94, 290), 08248 at 0°, 
and 0-8113 at 187°; 0-8138 (Apjohn); 0*8184 at 15° (CahoUrs); 0-8185 
at 13° (Rieckher); 0821 at 16° (Pelletan); 0*818 at 14° (Delffs, N,Jahrh. 
Pharm. 1, 1); Index of refraction for the red ray, 1-3601 (Delffs). — 
Boiling point: 125° at 0*76 met. atmospheric pressure (Pelletan) [too low 
in consequence of the presence of common alcohol]; 131° (Apjohn); 
131-5° (Dumas); 131-8 at 0751 met. (Pierre); 132° at 076 met. 
(Cahours); 133° at 27" 9'" and with platinum-wire immersed (Kopp); 
in a later experiment {Ann. Phai^m. 94, 289) Kopp found that a thermo- 
meter with its bulb immersed in the liquid showed, at the commencement 
of the ebullition, a temperature of 129*6^, and afterwards slowly rose; 
while a thermometer with its bulb in the vapour marked 130*9° at first 
and slowly rose to 131-6°, (these temperatures determined by Kopp, are 
corrected for the difi*erence of temperature of the mercury in the tube 
and bulb); 134° (Rieckher); 132° at 3397 Par. lines. (Delffs.) The 
active alcohol boils at 127° to 128°, nnder the ordinary pressure, and 
the inactive alcohol at 120°. The mixture of the two boils at interme- 
diate temperatures. (Pasteur.) — Specific heat 0-5873. Latent heat of 
vapour 121-37. (Favre and Silbemiann, N. Ann. Chim. Phys. 37, 461.) 
— Vapour-density: 3137 (Apjohn); 3147 (Dumas); 320 (Balard). 
The oil makes a transient grease-spot upon paper. (Pelletan.) Its odour 
is penetrating (Pelletan), repulsive (Dumas), peculiarly pungent (Apiohn); 
in the pure state it has a less disagreeable odour than when diluted. 
(Rieckher.) Its taste is persistently sharp and warm (Pelletan, Cahours); 
sharply bitter, somewhat like that of oil of cloves. (Apjohn.) The 
vapour when inhaled, or a drop of the liquid placed on the tongue, 
excites, in susceptible persons, coughing, nausea, giddiness, and fainting, 
and especially weakens the lower extremities, even for 24 hours. In 
dogs^ a few table-spoonsful merely produce vomiting; in rabbits, two tea- 
spoonsful excite vomiting, and larger doses produce oppression of the 
chest and death; still smaller animals are rendercfl insensible by a few 
drops, and asphyxiated and killed, with convulsions and interrupted 
respiration. Ammonia acts as an antidote. (Pelletan.) According to 



14 AMYLENE: PRiMAUT NUCLEUS VmK 

Schlossberffer (Ann. Fharm. 73, 212), amjlio alcohol acts apon the animal 
organism Tike vinic alcohol, being quicklj decomposed in the blood, 
producing intoxication and death-like sleep, and acting in the same 
manner on the mucous membranes. — Amylic alcohol is neutral. 

Dumas. Cahoun. Apjohn. Balard. Kopp. Pierre. 

10 C 60 .... 68-18 .... 68-95 .... 68-61 .... 68-13 .... 67-65 .... 67-68 .... 68-00 

12 H .... 12 .... 13-64 .... 13-60 .... 13-52 .... 13-33 .... 1375 .... 1367 .... 13-87 

2 O .... 16 .... 18-18 .... 17-45 .... 17*97 ... 18-54 .... 18-60 .... 1865 .... 18-13 

CMHUQS 88 .... 100-00 ....100-00 ....100-00 ....100 00 ...10000 ...lOO'OO ....10000 

Yol. Density. 

C-Tapour 10 4-1600 

H-gas 12 0-8316 

O-gas 1 1-1093 

Vapour of Amylic Alcohol 2 61009 

1 3-0504 

Decompositions, IT. 1. Amylic alcohol passed in the state of vapour 
through a long gla^s-tube at a moderate red heat, is resolved into pro- 
pylene gas and marsh gas in about equal volumes; a liquid also condenses 
which appears to be unaltered amylic alcohol. If the heat be too low, 
but little gas is formed; if it be too great, scarcely anything but marsh- 
gas is obtained. (Reynolds, Chem, Soc, Qu, «7, 3, 111; compare ix, 395.) IF 
— 2. Fusel-oil is difficult to set onfire^ and burns with a white luminous 
flame, leaving a small glutinous residue (Pelletan); bums with a pure blue 
flame (Cahours); with a bright smoky flame. (Apjohn.) — 3. It is not 
much altered by being kept for two years in bottles containing air, but 
acquires the power of reddening litmus slightly, in consequence of the 
formation of a volatile oily acid [valerianic acid 11 (Cahours.) — 
4. When fusel-oil bums in the glow lamp (ii, 56), a liquid condenses, 
which forms with potash a substance resembling the resin of aldehyde, 
but does not reduce silver-salts, or yield any crystalline product with 
ammonia. (Balard.) When heated platinum-black is moistened with 
fusel-oil, and covered with a glass bell-jar open at top and standing in a 
plate containing water, valerianic acid soon begins to run down the sides 
of the bell-jar into the plate. (Cahours.) 

CiOHWQs + O* = CWHWO* + 2H0. 

This transformation likewise takes place in vinegar manufactories, when 
brandy containing fusel-oil is used, so that sometimes the odour of vale- 
rianic acid is perceptible, only however at temperatures above 36°, while, 
below that point, anv fusel-oil that may be present is converted into 
acetate of amvl, which has not an unpleasant odour. (Dobereiner.) 
Fusel- oil may also be converted into valerianic acid by passing a stream 
of oxygen through it at a boiling heat, the apparatus being so arranged 
that the vapours which rise may be condensed and flow back again. 
(R. Railton, Chem. Soc. Qu, J, 6, 209.) 

5. When chlorine gas is passed for several hours through fusel-oil, the 
gas is abundantly absorbed, with great rise of temperature and evolution 
of hydrochloric acid, and the fusel-oil is converted into a compound 
resembling chloral. (Cahours.) — 6. When a solution of fusel-oil in a large 
quantity of wat^r containing a little potash, is treated with bromine or 
iodine, till those bodies are no longer decolorised, the liquid yields on 
evaporation a residue of valerate of potash. (Lefort, Compt. rend. 



AMYLIC ALCOHOL. 15 

23, 229.) — The solution of iodine in fnsel-oil turns acid from formation 
of hydriodic acid. (Rieckher.) 

7. Strong nitride acid dissolves fusel-oil with violent action, the liquid 
turning brown as the point of saturation is attained, and then yields by 
distillation, not valerianic acid, but a neutral oil, probably amylic aldide. 
(Dumas & Stas.) — Cold nitric acid does not mix with fusel^il or exert 
any action upon it; but on heating the liquid, till gas-bubbles begin to 
escape, decomposition takes place, which soon becomes rapid, even if the 
fire be quickly removed, but may be moderated by the addition of cold 
water. An oily mixture passes into the receiver, consisting of amylic 
ether, amylic aldide (inasmuch as potash forms with it a substance like 
aldehyde-resin, nitrate of amyl» and hydrocyanic acid; and in the retort 
there remains valerianic acid, probably mixed with the aldide, inasmuch 
as potash colours it deep brown. (Balard.) — 8. Fusel-oil is decomposed 
by aqueous iodic acid, slowly and without formation of carbonic acid. 
(Millon.) — 9. By aqueous chromic acid it is converted into valerate of 
amyl. — When an aqueous solution of bichromate of potash is added to 
a mixture of fusel-oil and strong sulphuric acid, an oil rises to the surflEuse 
consisting of amylic aldide (or rather, according to Balard, of valerate 
of amyl which is polymeric with it). (Duma« & Stas.) -^ A cold- 
saturated aqueous solution of bichromate of potash, supersaturated with 
oil of vitriol, becomes heated on addition of fusel-oil, and is converted 
into a mixture of valerianic acid and chrome-alum, with amylic aldide 
floating on the surface. (Balard.) — 10. With peroxide of manganese also, 
a mixture of fusel-oil and strong sulphuric acid yields amylic aldide 
(valerate of amyl). (Dumas & Stas). 

1 1 . Fusel-oil mixes readily with oil of vitriol, the mixture becoming 
thick and acquiring a carmine colour, and, on addition of water, the 
fusel-oil is again separated^ with pale yellow colour, but with its original 
odour. (Pelletan.) In this reaction, sulphamylic acid is produced and 
remains dissolved in the water. (Cahours.^ — On distilling the solution 
of fusel-oil in oil of vitriol, sulphurous acia is evolved, amylene (C*^N^°), 
and its multiples (C^H^ and C^H^), pass over, together with a sulphu- 
retted compound, and a black pitchy substance remains. (Balard.) 
By distillation, amylene is obtained [or chiefly rather C^H^, inasmuch 
as it boils at 160*^, together with valerianic ether, valerianic aldide, and 
a liquid having an ethereal odour, and strong but not bitter taste. 
(Graultier de Claubry.) — With a mixture of strong sulphuric and nitric 
acid, fusel-oil becomes so violently heated that the escaping vapours take 
Are spontaneously. (Rieckher.) — 12. Fusel-oil distilled with anhydrous 
phosphoric acid yields amylene and its multiples. (Balard.) 

13. By terchloride of phosphorus added in successive portions, fusel- 
oil is converted, with violent evolution of heat, into phosphate of amyl, 
chloride of amy], and hydrochloric acid. The latter escapes as gas 
together with part of the chloride of amyl : 

3C»H»03 + pci» « 2CWH»0,PH0* + C»0H"C1 + 2HCL 

By addition of excess of terchloride of phosphorus, which is taken up 
without further rise of temperature, and then of a small quantity of 
water, fusel-oil is completely converted into phosphate of amyl, a portion 
being however further transformed, by the phosphorous acid produced at 
the same time, into amylophosphorous acid. (Wurtz, iT. Ann, Chim, 
Phys, 16, 221.) — 14. With pentachloride of phosphomsy fusel-oil yields 



16 amylbnb: primary nucleus c^ohi^ 

chloride of amjl, chlorophosphoric and hjrdfochlorio acid; (Cahours, 
Compt. rend. 22, 486; 25, 727): 

CMHi^O* + PCl» « CMH"C1 + pa«o» + flCl. 

15. Fasel-oil absorbs kydrochJotic acid gas, witb rise of temperature 
ftnd brown colouring. — 16. Fusel-oil dissolves, with the aid of neat, in 
aqueous chloride of tine, forming a liquid which begins to boil at 130°, 
and yields a distillate of C^®H^° and C^H^ (separable hy fractional recti- 
fication at a gentle heat), which, when repeatedly distilled over chloride 
of zinc, are more and more converted into C^H^, perhaps by the con- 
tinned action of the heat. (Balard.) With chloride of zinc, a gas is 
likewise attained, baring the composition of ethylene. (Medlock.) — 
17. By distillation -wiihfitl/oride of boron or fltioride of silicium, amylene 
and its mnltiples are likewise obtained; on the other hand^ in all these 
oases, no aniylic ether, or but very little of it, appears to be formed. 
(Balard.) — 18. Fusel-oil distilled with phosphorus and h'omine, or iodine, 
yields bromide or iodide of amyl. 

19. Fusel-oil heated to 220° with a mixture of hydrate of potash and 
lime yields valerate of potash and hydrogen gas. (Dumas & Stas.) 

CioH<K)S + KO, HO = C^oH'KO* + 4H. 

The fusel-oil is heated in a retort; ten times its weight of potash-lime 
thrown upon It; and the mass, which spontaneously becomes warm and 
acquires a yellow colour by contact with the air, heated in a bath of 
fusible metal to 170° and then to 200°, which temperature is continued 
for 12 hours. At 170°, the mass turns white and begins to ^ive- off pure 
hydrogen gas, not mixed with any hydrocarbon, unless the heat be too 
suddenly raised. The residue containing the valerate of potash may be 
nltimately heated without residue to 230°. If, after cooling, it be exposed 
to the air, without being covered with water, it absorbs oxygen [and 
vapour of water ? ] with such avidity, that it burns away like tinder. 
(Dumas & Stas.) — Tf 20. Chloride of cyanogen is rapidly absorbed by 
fusel-oil, and exerts upon it an action similar to that which it produces 
upon common alcohol (viti, 256) sal-ammoniac gradually separating out, 
and the liquid yielding by distillation, first, chloride of amyl, which boils 
at about 100°, and then amylic urethane C"NH^'0* : 

ClOHBO* + C«NC1 + 2H0 = C«NH"0< + HCl. 

[The chloride of amyl is formed by the action of the hydrochloric acid 
on another portion of the amylic alcohol. The formation of chloride of 
ammonium indicates also that of carbonate of amyl, according to the 
equation : 

2C«'H»0« + C^NCl + 2H0 =*« NH*C1 + 2(C»0Hi»O,CO«) : 

but the formation of the latter compound was not actually observed]. 
(A. Wurtz, N. J. Pharm, 20, 14; Ann, Pharm, 79, 280) f. 

Combinations. — Fusel- oil shaken up with watery takes up a small 
quantity of it, increasing thereby in density. (Pelletan, Apjohn.) The 
water at the same time dissolves a small portion of the fusel-oil, acquiring 
its odour and diminishing somewhat in density. (Pelletan.) According 
to Apjohn and Balard, fusel-oil does not dissolve in water. 



VALERALDIDE. 17 

It dissolves phosphorus at a boiling heat, forming a lemon-yellow 
solution (in small quantity, according to Trautwein), from which the 
phosphorus does not separate out on cooling. (Pelletan.) 

It dissolves a small quantity of sidphur when heated (none, according 
to Trautwein, even at a boiling heat), the sulphur being precipitated on 
cooling. (Pelletan.) 

It dissolves iodine abundantly. (Pelletan, Trautwein, Repert, 91, 28.) 

It dissolves in strong hydrochloric add. (Balard.) 

It absorbs ammoniacal gas with green colour. (Pelletan.) 

It dissolves a large quantity of hydrate of potash, acquiring first a 
yellow, then a greenish, then a deep red colour, and an offensive odour. 
Water forms with this solution an emulsion, from which the fusel-oil 
separates. (Pelletan.) — With hydrate of soda it forms a red solution, and 
if it contains a little water, a buttery mass. (Pelletan.) 

It combines with chloride of calcium. 

With bichloride of tin, it assumes a red colour, and yields crystals, 
which are decomposed by water, slowly even by the moisture of the air, 
yielding aqueous bichloride of tin and unaltered fusel-oil. (Gerhardt, 
Ann. Chim. Phys. 72, 167.) 

From solution of gold, it extracts in a few days all the chloride of 
gold. (Pelletan.) 

It mixes with ether. (Pelletan.) 

It mixes in all proportions with alcohol (Apjohn), and is separated 
therefrom by water only, when the proportion of alcohol is small. 
(Pelletan.) This solution, and even brandy containing fusel-oil, assumes 
a carmine-colour when mixed with oil of vitriol. (Pelletan.) 

Fusel-oil mixes in all proportions with strong acetic acid, and is not 
separated therefrom by potash-ley, because it is soluble in aqueous 
acetate ofpolaUi. (Pelletan.) 

Fusel-oil mixes with oils both fixed and volatile^ dissolves solid /a<«, 
common camphor, many hard resins, and, at high temperatures only, a 
small quantity of caoutchouc. (Pelletan.) 



Valeraldide. 

Dumas & Stas. Ann. Chim. Phys. 73, 145; also J. pr, Chem. 21, 289. 
Gaultier de Claubrt. Compt. rend. 15, 171 j also Ann, Phann. 

44, 127. 
Trautwein. Repert, 91, 6. 

Chancel. Compt. rend. 21, 934; also J. pr. Chem. 36, 447. 
Keller. Ann, Pharm. 72, 31. 
Parkinson. Ann. Pharm, 90, 114; abstr. J, pr, Chem, 62, 286; Pharm, 

Centr, 1854, 569; Jahresbus 1854, 442. 

Valerianic Aldehyde,' ValeralpMjflaldid, Amylaldehyd, Baldrianaldehyd, Aldehyde 
valerique. 

Formatuni, 1. By the distillation of fusel-oil with oil of vitriol, 
(together with amylene and amylic ether.) (Gaultier.) — 2. By the action 
of strong nitric acid ^upon fusel- oil. (Dumas & Stas.) — 3. By the dry 
distillation of valerate of baryta. (Chancel.) — H 4. By the dry distillation 

TOL, XI. ^ 



18 AMTLENE: PRIMART NUCLEUS CWH»». 

6f a mixtare of ralerate and forniiate of lime in equal fiumbera 
of atoms : 

C»H«CaO« + C«HCaO< - 2(CaO,CO») + CW>H»0«. 

Similarly, any aldide may be obtained by distilliiig the lime or baryta- 
salt of the corresponding fatty acid with an equivalent quantity of the 
formiate. (Linipricht, Ann, F/iarm, 97| 368.) % — 5. In the distillation 
of bran with sulphuric acid and peroxide of manganese, many other 
products being formetl at the same time. (Keller.) When lupuUn, the yellow 
powder, which falls oat on rabbit'g the cones of the hop, is distiUed with water, Tale- 
rianic acid passt^s over U^ether with a volatile oil. The latter is resinised by contact 
with the air ; and the resinous ma^s distilled at a gentle heat with hydrate of lime yields 
▼aleraldide. (Personne, N. J. Pharm. 26, 241 ; Compt, rend. 38, 309.) 

Preparation, 1. The distillate obtained from fusel-oil aud oil of 
vitriol is repeatedly rectifieil, the less volatile liquids being each time set 
aside. (Gaultier.) — 2. The mixture of fusel -oil and strong nitric acid is 
saturated with an alkali, after the violent evolution of heat has subsided, 
then distilled, and the oil which passes over collected. (Dumas AStas.) — 
3. Peroxide of manganese or aqueous bichromate of potash is added to 
a mixture of fusel-oil and strong sulphuric acid, and the oil which rises 
to the surface taken off. (Dumas & Stas.) — Or, 4 At. peroxide of man-^ 
ganese are added to a cooled mixture of 1 At. fusel-oil and 4 At. strong 
sulphuric acid contained in a tubulated retort; the distillation, which at 
first goes on of itself, assisted towards the end by a gentle heat; the 
slightly acid distillate redistilled after addition of carbonate of potash; 
and the oil separated from the water which has passed over with it. 
(Trautwein.) %, Or, 11 pts. of pure amylic alcohol are gradually mixed 
with 16^ pts. oil of vitriol, previously diluted with an equal volume of 
water, and the mixture after cooling, gradually added to an aqueous 
solution of 12^ pts. of bichromate of potash in a tubulated retort, 
whereby sufficient heat is evolved to distil over the greater part of the 
liquid, external heat being required only towards the end of the opera- 
tion. The upper oily layer of the distillate is then separated from the 
lower liquid, washed with potash to free it from valerianic acid, and 
agitated with a perfectly saturated solution of bisulphite of soda, where* 
upon a crystalline compound of valeraldide with that salt separates out. 
The crystalline mass is then strongly pressed and dissolved in warm 
water at 70° to 80°; any oily liquid that may yet remain removed; the 
crystalline compound which separates on cooling, mixed in a retort with 
a concentrated solution of carbonate of potasa or soda, and gently 
heated; and the valeraldide which rises to the surface as an oily layer, 
distilled off, separated from the water which passes over with it, and 
rectified. (Parkinson.) % — 4. Valerate of baryta is distilled at a dull 
red heat, and the resulting oily mixture of about 9 pts. valeral and 1 pt. 
valerone repeatedly rectified, the valeral, which is the more volatile, 
being collected apart. (Chancel.) 

Properties, Oolourlese oil. (Dumas & Stas; Gaultier; Parkinson.) 
Mobile; of sp. gr. 0*820 at 22° (Chancel); 818 (Trautwein); 0*8009 at 
20°. (Personne.) — Boils at 96° (Gaultier), a little above 100 , and yields 
a vapour whose density is 2-93 (Chancel); at W° to 97^* (Parkinson); 
at about 90 ^ (Personne.) Smells like apples (Dumas <k Stas); has a 
fahl^rp penetrating odour (Gaultier); pleaeant, but gftrong and peculiarly 
suffocating (Parkinson); produces oppreesion when inhaled (Gaultier), 



VALERALDIDE. 19 

aDd excites coughing (Trautwein); its vapour diffused in an apartment 
smells fruity at first, afterwards like valerianic acid. (Trautwein.) Its 
taste is strongly bitter (Gaultier); burning (Chancel); sharp and bitter. 
(Parkinson.) Neutral. (Doinas & Stas.) Refracts light strongly. (Par« 
kiuson.) 

Dumas & Stas. Chancel. Keller. 

IOC 60 .... 69-77 ..... 70 07 .... 6956 .... 69*51 

10 H 10 ... 11-63 11-60 .... 11-54 .... 11-79 

2 O 16 .... 18-60 18-33 .... 18*90 .... 1870 

CU)HM>0= 86 .... 10000 10000 .... 10000 .... 100-00 

Vol. Density. ~ 

Cyapour 10 .... 4*1600 

H-gaa 10 .... 0-6930 

O-Gas 1 .... 1-1693 



Vapoar of Yaleraldide .... 2 .... 5-9623 

1 .... 2-9811 

Decompositions. 1. Yaleraldide is very inflammable and burns with 
a bright flame faintly bordered with blue. (Chancel.) — 2. In contact 
with oxygen gas and platinum -black, and by other oxidising agents, it Is 
convertea into valerianic acid. (Chancel.) Also by exposure to the air 
(Gerhardt, N, Ann. Chim. Phys. 7, 279; Parkinson); and when kept for 
a month in vessels containing air, it acquires the power of reddening 
litmus. (Trautwein.) — 3. By nitric acid of ordinary strength, it is 
converted, with violent evolution of nitrous vapour, nitric oxide, and a 
gas which burns with a very bright flame, into a liquid which sinks in 
water and appears to be nitrovalerianic acid. (Chancel.) — 4. When vale- 
raldide is heated with a dilute solution of bichromate of potash, valerianic 
acid passes over. — 5. When repeatedly distilleii with dilute sulphuric 
acid and peroxide of manganese, only a small portion of it is converted 
into valerianic acid. (Trautwein.) — 6. Fused with hydrate of potash, it 
gives off hydrogen and forms valerate of potasli. (Gerhardt.) 

CM»llMO» + KG + HO « C»H»KO* + 2H. 
Bat it is not decomposed by boiling with potash -ley of sp. gr. 1'338. (TVaotwein.) 

Combinations Insoluble in water. (Chancel, Parkinson). — Dissolves 
a tolerably large quantity of phosphojtts; no sulphur, even at the boiling 
heat; and a very large quantity of iodine. (Trautwein.) 

Mixes with oil of vitriol, (Gaulthier.) 

Yaleraldide ammonia. A mixture of valeraldide and aqueous ammonia, 
which is turbid at first, soon becomes dear and deposits a large nui^ber 
of shining octohedrons. These crystals contain a large quantity of water of 
crystallization, which they gradually lose in vacuo, over a mixtu/e of 
sal-ammoniac and lime. (Keller ) — IT. Yaleraldide absorbs ammoniacal 
gas rapidly and with great evolution of heat, producing a thick syrtip; 
which, after standing for some weeks, is converted into a mass of delicate 
prismatic crystals. By exposure to the air or by heat, these crystals are 
quickly reconverted into the syrupy liquid. They are insoluble in water, 
but dissolve readily in alcohol and ether. (Parkinson.) — According to 
Limprieht (Ann, Pharm. 90, 1 1 1 ), the valeraldide obtained by oxidation of fusel-oil forma 
a dc^nite compound with ammcnia ; but that which is produced by the dry distillation 
of valerate of baryta does not form any snch compound. Similarly with bntyraldide. 
Hence Limpricht concludes that the products obtained by the dry distillation of the 

c2 



to AMTLKXI: ftnUlX 5CTVXErS 




« ^,.>» 




JO 1^ ^> M 



NH*A^'ni»\>» lA!i . iiM^-^ - ^le- 
















VALBRUNIC ACID. 21 



Valerianic Acid. 

Chstbbul. Arm, OMm. Phys. 7, 264; 23, 22; also Sckw. 89, 79. 

Recherckes sur leg corps gr<Uf 99 and 200. 
Grots. Br. Arck, 33, 160; 38, 4. 
Tromm8I>orff. N. Tr. 24, 1, 134; 26, 1, 1; abstr. Ann. Pharm. 

6, 176. 
WiNCKLEB. Bepert, 44, 180; — 78, 70. 
Trautwein. Eoitn. Arch. 26, 982; Repert 91, 28. 
Dumas & Stas. Ann. Chim. Phyt. 7S, 128; also Ann. Pharm. 35, 145; 

also J. pr. ChevL 21, 278. 
Louis LuciEN Bonapabtb. J. Chim. mid. 18, 6, 6; also J. pr. Chem. 

30, 302. 
WiTTSTBiN. Repert. 87, 289; 
Iljbnko & Laskowskt. Ann. Pharm. 55, 78. 

Valeric acid, BiBidriaiu^ure, Delphinsi^e, Phoeentduref Aeide valeriamquet 
Ae. valerique, Ac. delphinique, Ac. phocenique. — First obtained from dolphin 

oil and exactly investigated bj Chevreal in 1817. The acid discovered 
in valerian root by Pentz (Br. A^ch. 28, 338) in 1819, and by Grote in 
1830, and specialij examined bj Trommsdorff, as also that obtained by 
Dnmas and Stas, from fusel -oil, were sooi^ recognized as identical with 
delphinic acid. 

Sources. 1. In YaUrian root. To the amoant of not quite 1 per cent. 
(Trautwein.) Both in the fresh and in dried root. (Grote.) It exists most 
abundantly in the small valerian root (Bopaparte), which is gathered in 
dry places in the sprinir. (Aschoff.) The herb of valerian contains very 
little acid. (Grote.) When the root is distilled with water, the acid 
passes over, partly in the state of aqueous solution, partly mixed with 
a neutral oil. 

2. In the ripe berries (Chevreul), and in the bark (Kn^mer, N. Br. 
Arch. 40, 269; More, Ann. Pharm. 55, 330), of Vibumvm Opulus, and 
in the alburnum of Samkucus ni^xL (Kramer, If. Br. Arch. 43, 2].) 

3. In the root of Angdiea Aixhangdica. (Meyer & Zenner, Ann^ 
Pharm. 55, 317) and of AUiomanta Oreddinum. (WiuQ^ler.) In Asa 
foBiida. (Hlasiwetz.) 

4. In the oils obtained by distillation of the flowers of Anihemis 
nohilis, the more volatile portion which distils below 210° consisting 
chiefly o\ an oil composed of C^H^, and the portion which distils at and 
above 210°, yielding, when heated fqr a short time with alcoholic potash, 
the rest of the oil C'^If , while valerate and angelate of potash remain 
behind. (G^rhardt, N. Ann. Chim. Phys. 24, 96.; also Ann. Pharm. 67, 
238; also J. pr. Chem. 45, 221; oon^p. Schindler. If. Br. Arch. 41, 32.)— 
Peretti, (J. Chim. mid. 21, 433) and Dumeuil (Repert. SQ, \76) likewise 
obtuned from the water distilled from the herb of Matricaria Parthenium, 
and of Artemisia Absinthium, a volatile acid w|iioh is perhaps valeri- 
anic acid. 

5. The herb of Digitalis purpurea and other scrophulariaoeous plants 
yielded to Pyr. Morin, (N. J. Pharm. 7, 299) a volatile acid, for which 



20 AMYLBNE: PRIMARY NUCLEUS C>*H'*. 

earthy propjrlates, butyrates, Talerates, &c. are not identical, but merely isomeric with 
the true aldidea produced by oxidation of the corresponding alcohols ? he accordingly 
di8ting;ui8hee them by the terms propylal, butyral, valeral, &c., restricting the term 
aldehyde [or aldide] to the bodies which form definite compounds of ammonia. He 
obserres, however that the butyral with which he experimented was contaminated with 
batyrone. (compare x» 551). 

Keller. Parkinson. 

10 C 60 .... 58-25 57-84 

N 14 .... 13-59 15-50 .... 13-41 

13 H 13 .... 12-62 12-84 

2 16 .... 15-54 13-82 

NH»,C»»H»«0» 103 .... 100-00 10000 

Valeraldide-AiDinonia is converted by sulphuretted hydrogen into yale- 
raldine C^NH*^$^^ a compound homologons with thialdine. (Beissenhirts, 
Ann, Fharm. 94, 109; Parkinson.) 

3(NH»,C»«H»«0«) + 6H8 = C»NH»S< + OHO + 2NH*S. 

Hydrocyanic acid, in presence of dilute hydrochloric acid, and with the 
aid of heat, converts valeraldide-ammonia into lencin. (Limpricht, Ann. 
Fharm. 94, 243; Parkinson); 

[NH»,C»H»0O» + C»NH + HCl + 2HO - C^n^HMCH + NH*Cl.] 

Valeraldide with BitvIphUe of JSoda. — PreparaHon. (p. 18.) — 
White crystalline mass consisting of nacreous iaminn. When left for 
some time in vacuo over oil of vitriol, it gives off its water of crystal- 
lization and crumbles to a white powder. When distilled with a con* 
centrated solution of carbonate of potash or soda, it gives off valeraldide. 
Dissolves sparingly in cold water, more readily in water of 70° to 80°. 
On heating the aaueous solution to between 80° and 90°, decomposition 
takes place, valeraldide and sulphurous acid beinff given off, and sulphite 
of soda remaining in solution. The compound is nearly insoluble in 
absolute alcohol and in ether. (Parkinson.) 

Parkinson. 
CiOHiOQS g6*o .... 43-17 

NaO 31-2 .... 15-66 15-46 

2 SO« 640 .... 32-13 31*95 

2 HO 18-0 .... 9-04 

C»H>«0>,NaO,280* + 2Aq 199-2 .... lOO'OO %. 

Valeraldide mixes in all proportions with alooholy etker, and volatile 
oUs. (Chancel.) 

It dissolves certain reniw. (Trautwein.) 

T Meimalerdldide T — According to Parkinson, valeraldide heated above Its boiling 
point, is converted into a liquid of the same composition, but boiling between 150*^ and 
200°; the same modification appears also to be present in the liquid expressed from the 
salphtte of soda compound, and is likewise separated when this compound is heated 
with dry carbonate of soda. Limpricht however did not obtain such a modification bj 
either o{ these three processes.^ 



VALBRUNIC ACID. 21 



Valerianic Acid. 

Chsyreul. Ann. Chim. Ph^s. 7, 264; 23, 22; also Schw. S9, 79. 

Beehei^ches nir les corps gra»y 99 and 200. 
Grots. Br. Arch. BS, 160; 38, 4. 
Trommbdorff. N.Tr. 24, 1, 134; 26, 1, 1; abatr. Arm. Pharm. 

6, 176. 
WiwcKLER. Eepert, 44, 180; — 78, 70. 
Trautwein. KaOn. Arch. 26, 882; ReperL 91, 28. 
Dumas & Stas. Ann. Chim. Phys. 73, 128; also Antk. Pharm. 35, 14d; 

also J. pr. Chem. 21, 278. 
Louis Lucien Bonaparte. J. Chim, mid. 18, 6, 6; also J. pr. Chem. 

30, 302. 
WiTTSTEiN. ReperL 87, 289; 
IiiJENKO k Laskowsjct. Anv» Pharm. 55, 78. 

Valerie acid, BMrianat^wrej DelphinMdftire, Phoeentdure^ Acide valerianique, 
Ac. valerique, Ae. deiphinigne, Ac. phoeemgue. — First obtained from dolpbin 
oil and exactly iavestigated by Chevrenl in 1817. The acid discovered 
in valerian root by Pentz (Br. Arch. 28, 338) in 1819, and by Grote in 
1830, and specially ei^amined by Trommsdqrn, as also that obtained by 
Dumas and Stas, from fusel -oil^i were sooi;^ recognized as identical with 
delphinic acid. 

Scurcee. 1. In Valerian rod. To the amount of not quite 1 per cent. 
(Trautwein.) Both in the fresh and in dried root (Grote.) It exists most 
abundantly in the small valerian root (Bopaparte), which is gathered in 
dry places in the sprini;. ( Aschoff. ) The herb of valerian contains very 
little acid. (Grote.) When the root is distilled with water, the acid 
passes over, partly in the state of aqueous solution, partly mixed with 
a neutral oil. 

2. In the ripe berries (Chevrenl), and in the bark (Knimer, iV. Br. 
Arch. 40, 269; More, Ann. Pharm. 55, 330), of Viburnum Opulus, and 
in the alburnum of Sam&uciu niff9*d. (Kramer, N. Br. Arch. 43, 21.) 

3. In the root of Angelica Aixhangelica. (Meyer & Zenner, Ann^ 
Pharm. 55, 317) and of AUiamanta Oreoselinum. (Winckler.) In Asa 
foUida. (Hlasiwetz.) 

4. In the oils obtained by distillation of the flowers of Anthemis 
nobUis, the more volatile portion which distils below 210° consisting 
chiefly of an oil composed of C^H", and the portion which distils at and 
above 210°, yielding, when heated fqr a short time with alcoholic potash, 
the rest of the oil C*^}^^\ while valerate and angelate of potash remain 
behind. (Gerhard t, 2^. Ann. Chim. Phys. 24, 96.; also Ann. Pharm. 67 f 
238; also J. pr. Chem. 45, 221; con^p. Schindler. y. Br. Arch. 41, 32.) — 
Peretti, (J. Chim. mid. 21, 433) and Dumeuil (Repert SB, 176) likewise 
obtained from the water distilled from the herb of Matricaria Parthenittm, 
and of Artemisia Absinthium, a volatile acid w|iioh is perhaps valeri- 
anic acid. 

5. The herb of Digitalis purpurea and other scrophnlariaceous plants 
yielded to Pyr. Morin, (N. J. Pharm. 7, 299) a volatile acid, for which 



22 amylene: (primary nucleus C"H", 

in case of its not being yalerianio acid, which it greatly resembles, 
he suggests the name : Antlrrhinic acid. 

6. As valerin, in the oil of Delphinus globiceps, and, although in much 
smaller quantity, in train-oil. (Chevreul.) Apparently also in animal 
secretions (Balard, iV. Ann, Ghim. Pht/s. 12, 317; see also Brendecke, 
Arch, Pharm, [2], 70, 34. 

7* Valerianic acid appears sometimes to exist in crude oil of amber. 
(Marrson, Arch, Pharm. [2], 72, 1.) 

Formation, 1. By the oxidation of fusel-oil, valeraldide, and various 
other compounds of the amylene series, by the action of the air, of nitric 
acid, chromic acid, hydrate of potash, &c. (Dumas & Stas, Balard.) — 
Hence also, when the residue of the distillation of wine-brandy, which 
contains fusel-oil, is left to putrefy in the air. (Balard, Laroque, N, J, 
Pharm, 10^ 103. Railton {Ghem, Soc, Qu. J, 6, 205,) finds that fusel-oil 
is converted into valerianic acid by passing a stream of oxygen gas 
through it. 

2. By the putrefaction of most azotised organic bodies. — When pnre 
casein is left to putrefy in summer in contact with water, valerate and 
butyrate of ammonia are formed, besides other productft. (Iljenko, Ann, 
Pharm. 63, 264; see also Brendecke, x, 79.) — The parings of very old 
Roquefort cheese yield, when distilled with dilute sulphuric acid, an acid 
which smells like valerianic acid. (Balard.) — Strong-smelling Limburg 
cheese contains valerate of ammonia besides other ammoniacal salts. 
(Iljenko & Laskowsky; camp, x, 79.) — Rebling observed that butyric 
and valerianic acid were formed, besides succinic acid, by the fermen^ 
tation of malate of lime, in contact with putrefying cheese, {Arch. Pharm. 
[2], 67, 300; Pharm, Centr, 1852, 63; in the latter place it is remarked 
that the valerianic acid may have been formed by the putrefaction of the 
cheeSe.) — Valerianic and butyric acid have been found in wheat spoiled 
by sea- water. (L. L. Bonaparte, x, 78.) — In the preparation of cartham in 
from safflower. thefe is sometimes formed in summer, a large quantity of 
valerianic acid, the carthamin at the same time diminishing considerably 
(Salv^tat, N. Ann. Ohim, Pht/s, 25, 337; also N.J, Pharm, 15, 269; idso 
J, pr, Chem, 46, 475.) Valerianic acid is likewise found in putrefied ox- 
bile. (L. A Buchner, J, pr, Chem. 46, 151.) It is also obtained by dis- 
tilling lupnlin with water. (Personne, p. 18.) 

3. By distilling gelatin (Schlieper, Ann. Pharm. 59, 1) or fibrin, 
albumin or casein (Guckelberger, Ann, Pharm, 64, 39), with chromate of 
potash and dilute sulphuric acid; and by the distillation of casein (Guck« 
elberger) or gluten (Keller, Ann. Pharm, 72^ 24) with sulphuric acid and 
oxide of manganese. 

4. When hydrate of potash i6 fused with leucin or casein till hydrogen 
is given off, as well as ammonia, a residue is left containing valerate of 
potash. (Liebig, Ann, Pharm, 57, 127.) — A certain quantity of this acid 
appears also to be formed when commercial indigo or lycopodinm seed is 
fused with hydrate of potash, probably in consequence of the protein- 
compounds contained in these oodles (vid, Gerhardt, iV. J. Pharm. 1, 
319; Winkler, Repert 78, 70). 

5. In the oxidation of oleic acid by nitric acid, and of certain hydro^ 
carbons by niti ic acid or hydrate of potash. When oleic acid is distilled 
with fuming nitric acid, a large quantity of valerianic acid distils over, 
together with many other acids. (Redtenbacher.) — The more volatile 
portion of the mixture of empyreumatic oils obtained in the distillation 



VALERIANIC ACID. 23 

of rape-oily jields, when distilled with strong nitric acid, a nnmber of 
acidsy amon^ which is valerianic acid; and when passed in the state of 
vapoar over heated soda-lime, it likewise forms a small quantity of Tale- 
rate, (Schneider^ Ann, Fhaitn. 10, 113.) 

Unsocceasfiil attempts to prpptre valerianic acid from acetic acid and Yalenan oil 
are described bj Trantwein. {Ka^tn, Arch,, 21, 459.) 

Preparation. 1. From Valerian root, -^ 1. The root is distilled with 
water; the acid oil separated from the water which distils over, and has 
likewise an acid reaction; the oil shaken up with water and carbonate of 
magnesia; the mixture distilled, whereupon a neutral oil passes over, and 
valerate of magnesia remains; and the valerianic acid separated from 
this salt bj distillation with sulphuric acid. The acid watery distillate is 
likewise neutralised with carbonate of soda; the solution evaporated in 
a basin, whereby the neutral oil is partly volatilissed, diffusing a strong 
odour of valerian, and is partly resinized to a brown film; the liquid 
filtered, and evaporated till it acquires a thickish consistence; this viscid 
liquid distilled with a quantity of oil of vitriol (diluted with one-half 
water) somewhat greater than is required to saturate the soda, the distil- 
lation being continued as long as the liquid which passes over continues 
to redden litmus; and the resulting layer of oil, which still contains a 
large quantity of water, decanted from the subjacent aqueous acid, and 
rectified by itself, the receiver being changed as soon as the clear oily 
anhydrous [mouobydrated] acid passes over in place of the milky liquid. 
(Trommsdorff.) — In this process there is sometimes left in the retort a 
small quantity of oil or resin, which does not show itself in a second 
distillation of the anhydrous acid; neither does any milky liquid pass 
over at the beginning. — The acid cannot be dehydrated by distillation 
over chloride of calcium without becoming contaminated with hydro- 
chloric acid. (Trommsdorff.) 

2. Twenty parts of the comminuted root are distilled with 100 pts. 
of water, till 30 pts. of distillate are obtained; 30 pts. of water added 
to the resiflue, and then distilled off; the same process repeated once 
more; the three distillates saturated with carbonate of soda, after sepa- 
ration of the oil; the mixture boiled down to 7 parts in a copper vessel; 
the residue evaporated to dryness in a porcelain basin; the solution of 
5 pts. of the residue in 5 pts. of water, mixed with 4 pts. oil of vitriol 
and 8 pts. water, and distilled nearly to dryness in a retort of eight times 
the capacity of the mixture; and the oily acid still containing water, 
removed from the watery distillate, and dehydrated by Trommsdorff's 
method. (Wittstein.) — After the three distillations with water, the root 
is exhausted of valerianic acid, but the residue is still strongly acid from 
the presence of a fixed organic acid (malic acid, according to Aschoff); 
there is therefore no necessity to add sulphuric acid for the purpose of 
separating the portion of valerianic acid supposed to be combined with 
baises. (wittstein.) -^3. One part of the root cut in pieces is rapidly 
distilled with 4 pts. of water till 2 pts. have passed over; 2 pts. of hot 
water added to the residue ; the distillation repeated ; and the same 
treatment continued as long as the water continues to pass over acid. 
The whole of the watery and oily distillate is then gradually mixed at 
the boiling heat witi| a quantity of carbonate of soda sufiicient to produce 
slight alkaline reaction; the liquid evaporate«l to about one-fourth, and 
filtered through coarse paper; the resinous powder whioh then remains, 
again boiled with aqueous carbonate of soda; th^ filtrate thence obtained 



24 AMYLENE: PRIMARY NUCLEUS C"Hw 

mixed with tbe preceding; and the mixtare, after evaporation to one- 
half, distilled nearly to dryness with oil of ritriol and salphate of soda, 
which serves to raise the boiling point. (Frederking, N". Br. Arch. 43,2.) 
— 4. The well bruised root is distilled with eight times its weight of 
water; the oil which passes over freed by milk of lime from the acid 
which it contains; the watery distillate, which contains by far the greater 
part of the acid, then saturated with this milk of lime; the aqueous solu- 
tion of valerate of lime mixed with a slight excess of lime and evaporated 
till a saline film forms on the surface, and decomposed in a stoppered 
bottle with excess of acetic acid; and the still coloured oily acid which 
rises to the surface, decanted off, and distilled at a gentle heat. (Bona- 
parte.) — Guillermond (Bev. scient. 19, 70,) extracts the acid from the oil 
with potash-ley. — 5. Sixteen parts of the root are boiled with water 
containing 1 pt. of carbonate of soda ; the liquid strained, with pressure; 
the residue boiled twice more with water; the three united decoctions 
distilled with 0*5 pt. oil of vitriol, till f of the liquid has passed over; 
and the distillate neutralised with carbonate of soda, evaporated down 
to a small quantity, and again distilled with sulphuric acid. This process 
yields 1*4 p.c. valerianic acid, that is to say, three times as much as is 
obtained by the troublesome distillation of the entire root. (T. & H. 
Smith, Pfiarm. J, Trans.; also iV. J. Pharm. 11, 16.) — 6. Winckler's 
mode of preparation, in which the watery distillate of the cold aqueous 
infusion of the root is saturated with oxide of lead, and then the lead- 
salt converted into a soda-salt by means of sulphate of soda, &c., &c., does 
not appear to present any advantages. 

The greater part of the valerianic acid contained in the root is united 
with a base which hinders the volatilisation. If therefore the root be 
distilled merely with water, it yields only 0*25 p.c. valerianic acid, and 
the residue distilled with water and sulphuric acid yields 0*75 p.c. more; 
100 pts. of the root should therefore be distilled with water and 2 pts. of 
oil of vitriol, till 300 pts. of distillate are obtained; the acid extracted 
from the separated oil with aqueous carbonate of soda; the watery portion 
of the distillate saturated with this liquid; the mixture evaporated down 
to 10 pts.; and the concentrated liquid distilled with a slight excess of 
sulphuric acid: this process yields from 0*9 tP 1*0 p.c. valerianic acid. 
(Rabourdin, N.J, Pharm. 6,310; Peretti, J. Chim. med. 21, 433.) — 
According to Aschoff, (iV. Br, Arch. 48, 274,) on the other hand, the 
distillation of the root with water and sulphuric acid yields apparently a 
little more valerianic acid than distillation with pure watek*, but only 
when the valerianic acid is contaminated with acetic acid and a small 
quantity of formic acid. The root should therefore be distilled with 
water alone, after one day's maceration ; if it be macerated for twenty 
days, fermentation takes place, and acetic acid is produced, which 
increases the yield of valerianic acid in appearance only. — Compare aUo 
Wittstein (p. 23.) 

The neutral part of the oil obtained by the distillation consists chiefly 
of the oil called borneene (0»H'«), and of another oil, valerol (C*»H*W), 
which crystallises near 0°, and, when exposed to the air, is converted into 
valerianic acid, with formation of carbonic acid. (Gerhardt, iV. Ann, Chim, 
Phys. 7*275.) — Accordingly, the distillate obtained from 100 pts. of the 
root, 10 pts. oil of vitriol, and 400 pts. of water, should be exposed to- the 
air for four weeks, after which, when saturated with hydrated oxide of zinc, 
it yields 1*5 pts. of valerate of zinc, whereas, if the air has not acted upon 
t, only 5 pt. of zino-salt is obtained. (Bnin-Buisson, N* J, Pharm., 9-97.) 



VALERIANIC ACID. 25" 

— The prodaot is rather diminished than increased hj exposure to the 
air, in either case, the quantity of zinc-salt obtained amounts to rather more 
than 0'5 p.c. of the root, and the oil which is removed from the surface 
of the liquid does not yield any more valerianic acid when exposed to 
the air or treated with nitric acid. (Laudet, N. J. Pkarm, 11, 444.) — 
The same oxidation is effected by chromic acid; 100 pts. of the root dis- 
tilled with 10 pts. oil of vitriol, 6 pts. of bichromate of potash, and 
500 pts. of water, — the 125 pts. which still pass over, and still contain a 
considerable quantity of unoxidised oil, being poured back again, — ^yield a 
distillate from which 1*8 pts. zinc salt are obtained. (Lefort, N, J, Pharm. 
10, 194.) — This process yields but a very small quantity of valerate 
of zinc, contaminated with sulphate of zinc and the zinc-salt of a pecu- 
liar acid produced by oxidation of the valerianic acid. (Laudet.) — 
Water distilled from the root and neutralised with baryta becomes acid 
again on exposure to the air, and so several times. Valerian-oil purified 
from all free acid and mixed with water, becomes sour in a few weeks 
when exposed to the air, but not in close vessels, and its mixture with 
strong potash ley- is completely converted into valerate of potash by 
exposure to the air for a year. The root contains therefore, not valerianic 
acid, but valeral (C^^H^^O'), which, when exposed to the air, especially in 
presence of water, and still more of alkalis, is converted by oxidation into 
valerianic acid. The root should therefore be mixed with potash-ley, and 
the mixture exposed to the air for four weeks, with frequent stirring, then 
distilled with sulphuric acid, &c., &c. (Thirault, JV. J. Pharm. 12, 161; 
comp. Righini, J, Chim. med, 21, 364; Lepage, N. J, Pharm. 9, 97.) 

II. From Angelica-toot, — The mother-liquor of angelic acid (x, 414) 
containing valerianic and acetic acid, is saturated with carbonate of 
baryta; the filtrate evaporated; the acetate of baryta extracted from the 
yellowish crystalline mass by alcohol; the portion which does not dissolve 
distilled with dilute sulphuric acid; and the valerianic acid which has 
passed over, freed from the still admixed angelic and acetic acid by satu- 
ration with ammonia and precipitation with nitrate of silver, whereupon 
the valerate of silrer, being the least soluble salt present, separates in the 
largest proportion. (Meyer and Zenner.) 

III. Ftom Dolphin-oil, — 4 pts. of dolphin-oil are heated in the 
water-bath with 1 pt. hydrate of potash and 4 pts. of water, till a uniform 
translucent mass is produced, which forms a clear solution with water; 
this solution decomposed by excess of tartaric aci<l; the watery liquid 
separated from the stearic, margaric, and oleic acids thereby eliminated; and 
this liquid distilled, together with the wash-water of these three acids (the 
distillate being rectified, if it leaves any residue on evaporation), then satu- 
rated with crystals of baryta, and evaporated, whereupon it yields valerate 
of baryta, a. Either 100 pts. of the dry baryta-salt are stirred up with 205 
pts. of phosphoric acid, of sp. gr. 1*12, in a narrow tube by means of a 
platinum wire ; and the valerianic acid which rises in the form of an oil 
above the separated phosphate of baryta, together with an aqueous solution 
of^id phosphate of baryta, removed with the pipette and distilled at a 
gentle heat, whereupon nearly anhydrous valerianic acid passes over 
together with a small quantity of a heavier stratum, and a small quantity 
of brownish valerianic acid, altered by the action of the air, remains in the 
retort. — b. Or, a mixture of 33*4 pts. oil of vitriol and 33*4 pts. water 
is poured upon iOO pts. of dry baryta-salt contained in the tube; the 
yellowish oily acid which rises to the surface removed by a pipette; 



26 AMYLENE: PRIMARY NUCLEUS C<«H<«. 

33*4 pU« more of water added to the restdae, whereby another portioa ol 
oily aoid is separated, and may be remoTed by the pipette; the whole of 
the decanted acid distilled in the water-bath, a thicl^ brownish yellow oil 
then remaining; and the acid which has passed over, separated from the 
watery layer. — For complete dehydration, 1 pt. of the acid is digested 
with 3 pts. chloride of calcium, and then dLscilled, whereby however the 
density is only reduced from 0*933 to 0*932 at 28^ (Chevreul.) 

IV. Frami. Ftusd-oU. — 1. A mixture of 1 pt. fusel-oil and 10 pts* 
potash-lime is heated in a retort placed in a bath of fusible metal, first to 
170°, then gradually to 200°, for 10 to 12 hours, till no more hydrogen is 
evolved; the mass left to cool in the closed retort; the retort then broken, 
and water quickly poured upon the mass, because it rapidly absorbs 
oxygen from the air and bums like tinder; the aqueous mixture poured 
into a new retort and distilled with dilute sulphuric acid; the valerianic 
acid collected in a receiver oontaininsc aqueous carbonate of soda; the 
valerate of soda thus obtained freed from undecomposed fusel-oil and 
valeraldide by boiling in a retort; and the valerianic aoid, after addition 
of excess of phosphoric acid, distilled into a fresh receiver, and freed 
from the water which first passes over by a second rectification, the 
receiver being again changed. (Dumas and Stas.) [Why is not the fasel-oil, 
after being heated with potash-lime, immediately distilled with water and sulphuric acid 
in the first retort?]. — 2. A cold-satu rated aqueous solution of bichromate of 
potash is mixed with oil of vitriol and then with fusel-oil, which is 
thereby converted, with evolution of heat and formation of chrome-alum, 
into valerianic acid and valerate of amyl which floats on the surface. 
The aqueous acid then yields by distillation the anhydrous [monohy- 
dratedj acid ; and the valerate of amyl distilled with potash yieldiif 
valerate of potash and fusel-oil, which may then be treated as before. 
(Balard, N.Ann. Chim. Phys, 12, 317.) — 3. Three atoms of coarsely- 
pounded bichromate of potash are mlxea in a tubulated retort with 38 At. 
water; a mixture of 7 At. oil of vitriol and 1 At. fusel-oil poured in 
through an S-tube dipping into the water, rather quickly at first, but 
afterwards by drops as the mixture becomes hot; the mixture heated 
after the spontaneous evolution of heat has ceased, till a quantity of 
watery liquid and valeraldide, equal to 1^ times the weight of the 
fnsel-oil, has passed into the receiver; water poured upon the residue, and 
the distillation repeated; the whole neutralised by agitation with calcine«l 
magnesia; the valerate of amyl decanted oft*; the aqueous solution of vale- 
rianic acid and acetate of magnesia evaporated and mixed when cold with 
oil of vitriol diluted with a twofold quantity of water; and the valerianic acid 
which rises to the surface, pipetted ofiT from the solution of sulphate of 
magnesia^ in which the greater part of the acetic acid remains dissolved, 
and repeatedly rectified, with separation of the water and the heavier 
acetic acid fvaleriauio acid containing a larger proportion of water 1], 
till its specific gravity is reduced to 0*930 at 17*5. There is also formed 
in the first retort a greyish green, porous, resinous mass of chromic valerate, 
which, after being collected on linen and washed with water, yields, hy 
distillation with dilute sulphuric acid, an additional quantity of valerianic 
acid, to be purified by rectification. liy this process, 2 pts. of fusel-oil 
yield in all, nearly 1 pt, of valerianic acid. (Trautwein, Hepert, 91, 12.) — 
According to the equation : 

3C"»H"0« f 4{KO,2CrO') + leSO' « 3CWH»0^ + 'l(KO,SO» + Cr80*,3SO») +CHO, 



▼ALKRIANIC ACID. 27 

3 At. fasel-oil shonld require 4 At. bicshromate of potash and 4 At. 
oil of vitriol, and shonld yield 3 At. valerianic aoid; in Trautvein's 
process, the chromic acts in excess at the beginning, and a portion of 
the valerianic acid is thereby further decomposed. — IT. H. Qrnneberg 
((71 pr, Ckem. 60, 169) pours 4^ ponnds of water on 2| pounds of chro- 
mate of potash in a retort, and allows a cooled mixture of 1 lb. fusel- 
oil and 4 lbs. oil of vitriol diluted with 2 lbs. water to run into the retort 
in a thin stream; he then distils once and calculates on a product of 
9 oz. (18 loth.) of oily valerianic acid. H. 

To separate a mixture of valerianic and butyric acids, it must be 
partially neutralized with potash and distilled. The butyric acid passes 
over, while valerate of potash remains behind; if too much potash be 
used, a certain quantity of butyrate of potash likewise remains; if the 
quantity of potash be too small, a portion of the valerianic acid likewise 
passes over; but the portion which remains mixed may be separated by a 
repetition of the process. If the valerianic (or butyric) acid is mixed 
with acetic acid, the latter remains as acid acetate of potash, when the 
liquid is partially saturated with potash and distilled, while the valeri- 
•anic (or butyric) acid passes over. This is connected with the fact that 
valerianic acid does not dissolve in aqueous acid acetate of potash more 
abundantly than in water, but dissolves very abundantly in a solution of 
the neutral acetate, whereby acid acetate and neutral valerate of potash 
are produced. (Liebig, Ann, Pharm. 70, 352.) 

Propertiei, Mobile, colourless oil. (Chevreul,. Tromnisdorff, & others.) 
Does not solidify at — 15** (Dumas & Stas; not even at — 21°. (Tromms- 
dorff.) [The acid, which according to Grote, became turbid at ~ 8* and solidified in 
an unctnoas maas at — 12'5'» probably containing water.] Sp. gr. 0*930 at 12*5® 

(Trautwein), 0-932 at 28"* (Chevreul), 0-937 at 16 5*» (Dumas A Stas), 
0-944 at 10° (Trommsdorff), 0935 at 15°. (Delffs.) Index of refraction, 
for the red ray = 1*3952. (Delffs.) The acid leaves oily spots on paper, 
which gradually disappear on the application of heat. (Trommsdorff.) It 
boils at 132° under a pressure of 27*5 inches (Trommsdorff), at 175° 
(Dumas & Stas), at 176 (Bonaparte), at 174-5°, with the barometer at 
237'8 mm. (Delffs.) [Trotnmsdorff's acid probably contained water, a conclusion 
warranted by its greater specific gratity.] Vapour>density = 3*67. (Dumas fit 

Stas.) The true density is not attained till the temperature rises considerably above 
the boiling point, the density at lower tempemtures appearing much too high. (Cabonts, 
▼ii, 54, 5.'>.} — The acid has an aromatic odour, like that of butyric acid, 
acetic acid and stale dolphin-oil, and imparts to fabrics moistened with it, 
the offensive odour of stale dolphin oil. (Chevreul.) Its odour differs 
somewhat from that of valerian -oil, and strongly excites coughin;^, espe- 
cially when the acid is heated. (Grote.) Smells strongly and persistently 
like valerian (Dnmas & Stas); smells more disagreeably than valerian, 
and at the same time like decayed cheese. (Wittstein, Nickles.) — Has a 
very burning sour taste with an aromatically sweet after-taste, like that 
of apples or nitrous ether, and leaves a white spot on the tongue. 
(Chevreul.) Its taste is sour, sharp, and repulsive, and leaves a lasting 
impression on the tongue ; but after dilution with water, it tastes less 
sharp and leaves a sweet after- taste (Trommsdorff); tastes very sonr and 
sharp, and produces on the tongue and lips, a painful burning sensation, 
white spots, aud shrinking and solution of the skin. (Grote.) Tastes 
very aoid and pungent, and leaves white spots on the tongue. (Dumas & 



28 AMYLBNE; PRIMARY NUCLEUS C'*H>*. 

Stas.) 'Reddens litmus strongly (Cheyreul); the reddening of the litnins- 
paper gradually disappears in a warm plaoe. (Trommsdorff.) 





The oily acid. 




Ettling. 


Dumas & galT^tat. 

StaS. OBITCWU 


IOC .... 


60 .... 


58-82 ... 


58-35 


.... 59-25 .... 58-77 


10 H .... 


10 .... 


9-81 ... 
31-37 ... 


10-02 

31-63 


.... 9-85 .... 9-72 


4 O .... 


32 .... 


.... 30-90 .... 31'51 








eiOHioo4 


102 .... 


10000 ... 


100-00 


.... 100-00 .... 100-00 




C-¥apour 

H.gM 




Vol. 

10 

10 


Denrity. 
.... 41600 
.... 0-6930 




O-gas 




2 


.... 2-2186 




Add-^apour . 




2 


.... 7-0716 






I 


.... 3-5358 



Ettling examined the acid prepared by Trommsdorf from valerian ; SaW^tat that 
obtained from safflower. 

The radical-theory likewise distiognishes a hypothetical anhydrous acid » 

CMH»0» « V"a. 

DecomposUions, IT. I. The vapour of the acid passed through a red- 
hot tube yields volatile products varying in quantity with the heat applied, 
and a large quantity of gas containing carhonio acid, carhonic oxide, 
hydrocarbons of the formula C°H°, and perhaps also in some experiments, 
marsh-gas. By ahsorhing the hydrocarbons with bromine- vapour, an oily 
liquid is ohtained which begins to hoil at 130^, and distils over for the 
most part between 186° and 1.56^ The rectification of this latter dis- 
tillate yielded a liquid boiling between 143" and 1 45°, and agreeing in 
composition very nearly with the formula C'H'Br*. (compare ix, 395.) The 
bromine-compound which distils over at the lower temperature is C'H^Br*; 
and the G'H'Br' appears to be mixed with a small quantity of C'H'Br*. 
The hydrocarbons formed in the decomposition of valerianic acid by heat 
are therefore ethylene, propylene, and perhaps also butylene. (A. W. 
Hofmann, Chem. Soc. Qu, J. 3, 210) % — 2. By distillation in vessels 
containing air^ part of the acid is converted into an aromatic substance 
resembling that which is obtained in the dry distillation of valerates; 
this substance remains dissolved in the undocomposed acid which passes 
over, and may be obtained separately by redistilling the distillate with 
oxide of lead. (Chevreul). — 8. The acid kept in a bottle containing air, 
slowly decomposes and acquires the odour of leather saturated with 
train-oil. (Chevreul.) — 4. When set on fire, it burjhs like a volatile oil 
(Chevreul); with a bright flame and without smoke or residue (Tromms- 
dorff); with a white sooty flame. (Dumas «fe Stas.) — 5. By chloiine gas, 
it is converted, with great rise of temperature and formation of hydro- 
chloric acid, in the dark into torch loro- valerianic acid, and in sunshine 
into quadrichloro- valerianic acid. (Dumas & Stas.) — By iodine and 
bromine it is not decomposed, even in sunshine (Dumas & Stas); by 
fuming nitric acid also, with which it mixes in all proportions, it is not 
decomposed, even on boiling, distillation, and cohobation. (Trommsdorff, 
Trantwein, Dnmas <fe Stas.) %. According to Dessaignes {Compt. rend. 
33, 164; Ann, Pharm. 79, 374), when valerianic acid is boiled for 18 
days with hjpdrated nitric acid, fsp. gr. 1*525 ?] in such a manner that 
the condensed vapours may flow back again, the nitric acid also being 



YALERIANTC ACID. 29 

renewed from time to time, a portion only of the ralerianic acid is 
decomposed ; and of the products of its decomposition, the most aban« 
dant 18 an acid which, from its analysis, appears to be nttrovcUfrianic acid 
C^'^H'NO* but in physical properties agrees rather with nitro-atigelic acid 
C^H^NO'. This acid is produced, whether the valerianic acid used is of 
natural origin or preparea from fnseUoil. When the natural acid is used, 
there are likewise formed a deliquescent acid, and a neutral, crystalline, 
azotised body having a faint odour of camphor; the artificial acid alsd 
yields a neutral, azotised oil having the odour of camphor IT. — 6. When 
valerianic acid is boiled with aqueous perchloric acidy no detonation takes 
place, but the valerianic acid which floats on the surface, acquires- a 
yellow and afterwards a brown colour. (Trautwein.) — 7. Its solution in 
ail of vitriol becomes slightly coloured at 100^ boils at a stronger heat, 
with evolution of valerianic acid and sulphurous acid, then slowly 
blackens, emits an ethereal odour, and leaves a tolerably large quantity 
of charcoal. (Chevreul.) The pale red mixture when boiled, gives olF 
the greater part of its acid undecomposed, together with small quantities 
of water and sulphurous acid; but there remains a small quantity of 
carbonaceous matter. (Trautwein.) The dark yellow mixture of the acid 
with fuming oil of vitriol gives off sulphurous acid and chars when 
heated. (Trommsdorff. ) — 8. Valeriauic acid heated with anhydrous phos- 
phoric acid is resolved into valeronc and combustible gases. (Dumas & 

Stas.) For the decompositions of yalerianic acid combined with potash and baryta by 
electricity and by heat, see these salts. 

ComlniuUions. With uHMter. — a Bihf/drated Valerianic acid, T>rky» 
drate of Valerianic acid* accordini^ to the radical- theory, which assumes the existence 
of IHO in the dry acid. The dry acid shaken up with a quantity of water 
much less than sufficient to dissolve it, takes up about 25 per cent, of 
water without losing its oily consistency, and rises to the surface of the 
excess of water which holds a portion of the acid in solution. (Tromms- 
dorff.) The same oil rises to the surface when a valerate dissolved in 
water is decomposed by a stronger acid, or when a large quantity of 
syrupy phosphoric acid is added to the aqueous solution of the acid; 
(J)uma8 & Stas.) It likewise passes over when a valerate is distilled with 
dilute sulphuric or phosphoric acid. This hydrate has a higher specific 

fravity than the dry acid, = 0'950 according to Trautwein, and a lower 
oiling point. (Dumas & Stas.) 

Dumas & Stas. Iljenko&Laskowsky. 

IOC 60 .... 50 .... 50-5 49-61 

12 H 12 .... 10 .... 101 9-76 

6 48 .... 40 .... 39-4 40*63 

C»HW>0*,2H0 120 .... 100 .... 1000 10000 

h. Aqueout Valerianic acid, — The acid dissolves in 16 pts. ol cold 
water (6rote)j in 20 pts. (Wittstein); in 30 pts. of water at 18*2'' 
(Chevreul^; in 30 pts. of water at 12''. (Trommsdorff.) The solution has 
a much milder taste than the dry acid, and saccharine at the same time. 
(Wittstein.) 

Dry valerianic acid dissolves a rather large quantity of phosphorus^ 
being gradually rendered milky thereby. (Trautwein.) 

It does not dissolve sulphur, even on boiling. 

It mixes with oil of vitriol, producing rise of temperature, and is 
partly separated therefrom by addition of water. (Chevreul) The solution 



30 AMYLENE: PRIMARY NUCLEUS e*H^ 

is pale rose-coloured. (Trautweln.) That formed with famiog salphurio 
acid is of a deep yellow colour; the acid likewise dissolves readily in 
heated sulphuric acid of sp. gr. 1*5. (Tronimsdorff.) 

It dissolves iodine quietly, abuudantly, and without erolution of heat, 
forming a brown-red solution (Trautwein); the solution saturated as com- 
pletely as possible, has a deep yellow-brown colour, and on addition of 
water, deposits all the iodine, while a dark yellow liquid remains. 
(Trommsdorff.) 

It mixes in all proportions with bromine. (Trautwein, Dumas &Stas.) 
It mixes in all proportions with fuming nitric acid (Trautwein); difr- 
solves sparingly in cold nitric acid of 35° Bm. (Chevreul.) 

The Valerates or Valerianates are, for the most part, = C^^H'MO*. 
They are somewhat unctuous to the touch. In the dry state, they are 
inodorous, even at 1 00°; but when moist, especially if heated or exposed 
to the action of carbonic acid, they emit the odour of valerianic acid. 
(Chevreul.) They have a sweet taste, especially the valerates of the 
alkalis and earths (Grote, Dumas, & Stas), and a pungent after-taste. 
(Trommsdorff.) Those valerates which are soluble in water have a 
slight acid reaction. ( Winckler.) When subjected to dry distillation, the 
vaJerates first give off undecomposed acid (Trommsdorff), then combustible 
gas, valeral and valertme. (CLnncel ) They are decomposed, with separa- 
tion of the oily acid, by phosphoric, sulphuric, hydrochloric, nitric, 
arsenic, acetic, succinic, malic, tartaric and citric acid, but not by benzoic 
acid. (Grote, Trommsdorff.) Many dissolve in water, some also in alc-ohol. 
(Trommsdorff.) 

Val'raU of Ammonia, — Valerianic acid forms with ammoniacal gas, 
crystals, which, when they take up a large quantity of ammonia, slowly 
deliquesce to a transparent and colonrless syrup. (Chevreul.) The aqueous 
acid snpersaturated with aqueous ammonia gives off ammonia when 
evaporated, and leaves an acid syrup, which, when supersaturated with 
ammonia and exposed to the air, solidifies in white needles united in 
radiated masses. These crystals have the odour of valerian, and a eweet, 
afterwards sharp taste like that of valerian ; they turn acid on exposure 
to the air, melt very easily, and volatilise in white fumes, leaving a trace 
of cliarcoal. (Trommsdorff.) The acid saturated with dry ammoniacal 
>ras and freed from excess of ammonia by gentle evaporation, solidifies in 
delicate, feathery, slightly acid crystals, which melt in a retort at di°C. 
without evolution of ammonia; and then emit white acid fumes, condens- 
ing in drops which crystallise when brought in contact with ammoniacal 
gas. (Aschoff, N , Br. Arch,, 48, 27-».) The dry salt is resolved by 
anhydrous phosphoric acid into valeronitrile (C^^NH*) and water. (Dumas, 
Compt, rend. 25, 442.) It dissolves very readily in water and likewise 
in alcohol. (Trommsdorff.) 

Valerate of FofasJi, — Potassium, gradually added to the dry acid, 
forms, with great rise of temperature and brisk evolution of hydrogen, a 
pulp, which on cooling solidifies in a mass consisting chiefly of valerate of 
potash. (Trommsdorff, Trautwein). — An aqueous solution of carbonate of 
potash slightly supersaturated with the acid, is evaporated, whereupon not 
only the excess of acid escapes, but likewise that which is expelled by the 
carbonic acid of tlie aJr ; the residue is dissolved in alcohol, the solution 
filtered from the carbonate of lime; and the filtrate evaporated. (Chevreul.) 



VALERIANIC ACID. 31 

Orote and TrommfdoHT omit the extraction with alcohol. The eolation evaporated 
to a Bjmp doee not crystallise but solidifies to a stiff paste (Grote); and 
leaves on farther evaporation, a white saline mass (Trommsdorff); a gam. 
(Damas & Stas.) The salt has a pnngent, slightly alkaline taste, with a 
sweetish after-taste^ and blues reddened litmus. (Chevreul.) 

Anhydrous, Chevreu). TrommsdorfT. 

KO 47-2 .... 33-67 34-47 33*7 

C»H*0« 930 .... 66-33 

C^H'KO* 1402 .... 100-00 

The salt melts with loss of water at 140°; blackens as the heat 
increases, and gives off vapours which smell at first of valerianic, after- 
wards of empyreumatic acetic acid and burn with a dense yellow flame; 
and leaves white carbonate of potash. (Trommsdorff.) The salt dissolved 
in water is decomposed, by the current of Bnnsen*s battery, into hydrogen 
gas, butylene, carbonic acid gas, an oily mixture of valyl and a compound 
ether, and carbonate of potash. (Kolbe.) Into a glass cylinder 1 1 inches 
deep and 2^ in. wide, is introduced a piece of copper foil, bent in a 
cylindrical form, touching the sides of the vessel, and having a copper 
wire proceeding from it, — and a thinner cylinder of platinum foil not 
touching the copper and having a platinum wire proceeding from it; the 
glass cylinder is closed with an airtight-fitting cork, through which pass 
the copper wire, the platinum wire, and a tube for pouring in the satu- 
rated aqueous solution of the pure salt (especially free from chlorine- 
compounds), and afterwards for letting oat and receiving the evolved 
gas; and the wires are connected with the poles of a four-celled Hansen's 
battery, the positive electricity entering by the platinum cylinder. A 
large quantity of hydrogen gas thus collects on the copper, together 
with monocarbonate and bicarbonate of potash, and on the platinum 
cylinder carbonic acid and butylene gases (x, 6C) together with valeri- 
anic acid, and a neutral oil which rises in drops, and appears to be a 
mixture of valyl [butyl] = C*H* [or rather = C"H**] with a compound 
ether of valerianic acid, probably valerate of butyl. (Kolbe, Ann. Fharm. 
70, 316.) Valerate of potash distilled with arsenious acid yields an 
oily liquid having a disagreeable alliaceous odour, and resembling 
cacodyl. (Gibbs, Ann, Phnrm. 86, 222. )|The salt deliquesces very quickly 
in damp air (slowly, according to Trommsdorff), dissolves very readily 
in strong alcohol, and at 20^ in less than 3*9 pts. of absolute alcohol. 
(Chevreul.) 

Valerate of Soda, — Prepared by Chevreul and Trommsdorff in the mme 
nanner as potash-salt* The sol ution e%'aporated to a syrup crystall ises to a 
cauliflower-like mass; bat, on account of the great deliquescence of the saJt^ 
only by spontaneous evaporation in dry air at 32** (not at "26°). (Chevreul.) 
So likewise in the drying chamber; but by evaporation at a stronger 
beat, there is obtained a white mass, which is unctuous to the touch; 
testes sweet and like valerian; becomes very soft at 130°; melts at 140° 
without loss of acid, to a transparent and colourless liquid, solidifies to a 
white mass on cooling; and is decomposed like the potash- salt at a 
stronger beat. (Trommsdorff.) By the galvanic current, it is decompoeed 
in the same manner as the potash- salt, but the bicarbonate of soda being 
but sparingly soluble and therefore more abundantly deposited, stops the 
current sooner. (Kolbe.) — The salt deliquesces in the air, and dissolves 



32 amylkne: primary nucleus C'*H«». 

very readily and abundantlj in water and in alcohol, even when absolute. 
(Cbevreul, Trommsdorff.) According to Trautwein, the evaporated 
Bolntion solidifies in a radiated mass. 

Valerate of Baryta. — Baryta- water neutralised with valerianic acid 
yields by spontaneous evaporation, transparent, shining, easily friable 
prisms (soft to the touchy according to Chanctl) which grate between the 
teeth, have a warm, pungently alkaline taste, with a sweetish after-taste 
like that of valerian ; slightly blue reddeued litmus (from containing 
baryta set free by the evaporation: C^uincel); and effloresce in the air 
between 20° and 25°j with loss of 2*41 p. c. water. (Chevreul.) The 
crystals contain 9*5 p. c. (2 At.) water of crystallisation, of which they 
give off from 2 to 2*5 p. c. on exposure to the air, and the rest at a higher 
temperature. (Chancel.) In the cold the prisms are permanent. 
(Trommsdorff.) 



BaO 

10 C 


Dried at nii\ 

76-6 .... 

60'0 .... 


45*16 ... 

35*38 ... 

5*;u ... 

14-15 ... 


Ettling. 

45-23 

35*59 

5*28 

13-90 


Chevreul. 
.... 45-29 


9 H 


9-0 .... 




3 


240 .... 










C»H»BaOV. 


169*6 .... 


100-00 ... 


100-00 





The dry salt begins to decompose above 250''^ and is completely 
decomposed at a dull red heat, with continued evolution of a gas, probably 
butyleno, which bums with a very bright flame, and a small quantity of 
pale yellow, strongly smelling distillate, which contains 70*7 p. c. C, 11*7 
H, and 17*6 O, and may be regarded as a mixture of 9 pts. vaieral (p. 17) 
and 1 pt. valerone (C^^H^O'), while carbonate of baryta remains, mixed 
with a small quantity of charcoal. (Chancel.) 

2CWH«BaO* - C«H»*0» + 2(BaO,CO»); 

but by the high temperature required for the decomposition of the baryta- 
salt, the greater part of the valerone (C^'H^H)') is resolved into vaieral 
Cioj^ioQ2^ and butylene (C*H»). (Chancel). Chevreul obtained, together 
with a gas which he regarded as ethylene, a very small quantity of car- 
bonic acid gas, an orange-yellow, strongly smelling liquid not acid or 
soluble in pota«h, and carbonate of baryta mixed with charcoal, amounting 
to 3*3 p. c. (of the valerate of baryta). — The salt heated in the air emits 
an odour like that of the Labiatce. The dilute aqueous solution, when 
exposed to the air, deposits carbonate of baryta and flakes, and acquires 
the odour of Roquefort cheese. The salt dissolves in 2 pts. of water at 15°, 
and in 1 pt. water at 20^. (Chevreul.) It moves about on water like buty- 
rate of baryta. (Larocque & Huraut.) It dissolves with difficulty in 
absolute alcohol. (Schlieper, Ann. Phartn., 5d, 21.) 

Valerate of Strontia, — Strontia-water neutralised with the acid 
deposits a varnish-like residue when evaporated in the open air, but 
within a bell-jar containing air over lime, it yields long efflorescent prisms, 
which smell of valerianic acid; taste like the baryta-salt; dissolve very 
readily in water; and, in the dehydrated state, contain 36*54 per cent, of 
strontia. (Chevreul.) The saturated solution of carbonate of strontia in 
a warm mixture of 1 pt. acid and 1 2 pts. water, yields by gentle evapo- 
ration, elongated four-sided tables, which effloresce in warm air, and are 
soluble in alcohol. (Trommsdorff.) 



VALERIANIC ACID; 33 

Valerate of Lime. -^ The aqueous acid eattirated at a moderate lieafc 
with carbonate of lime yields prisms and needles by slow evaporation. 
(Chevreul.) The «ry8tals are united in stars; taste sweetish; effloresco 
only in warm air; soften at 149°; melt at 150'', with blackening and 
evolution of vapours, which bum with a bright flame, and leave carbo^ 
nato of lime mixed with charcoaL They dissolve readily in water, and 
in boiling hydrated alcohol, sparingly in absolute alcohol. (Trommsdorff.) 
The crystals give oflT Q'G p. c. watej below 140^ (Winckler.) 

. Dried at 130®. Trommsdorflf. Chevreul. 

CaO 28 .... 23-14 2338 .... 21-48 

CWH90» 93 .... 76-86 

CJ«H9CaCM 121 .... 10000 

Valet'cUe of Ifagnesla. — The aqueous acid saturated with carbonate 
of magnesia forms a neuti-al, very sweet solution, which by quick evapo- 
ration yields saline crusts; but by slow evaporation transparent prisms 
united in tufts. These crystals effloresce only in warm dry air, soften at 
140^ then turn black and give off acid, and, after long ignition, leave 
pure magnesia. They dissolve pretty readily in water, sparingly in 
alcohol. (Trommsdorn.) 

Valerate of Glucina.'^^he solution of carbonate of glucina in the 
aqueous acid tastes very sweet, with a somewhat astringent after-taste, 
and leaves on evaporation, first a tough film, then a gummy mass perma- 
nent in the air. (Trommsdorff.) 

Valerate of Alumina, •— Hydrate of alumina quickly absorbs the dry 
acid, forming a mass which gives up nothing to boiling water; the same 
mass is formed on bringing hydrate of alumina into the heated aqueous 
acid, or by precipitating sulphate or hydrochlorate of alumina with 
valerate of potash. This mass treated with hot water divides into flakes 
which quickly settle to the bottom, and on cooling solidify in a tallowy, 
very friable mass, having a slightly sweet taste. This mass dried at 
130'', 4y>ntains 15*26 p. c. alumina. Boiling water and aqueous valerianic 
acid dissolve only a trace of it; alcohol none. (Trommsdorff.) 

Valerate of Zirconia. — The earth dissolves only in the boiling 
aqueous acid, and but very sparingly; the solution has a sweetish taste, 
reddens litmus strongly, and on evaporation gives ofl* acid and leaves a 
dry, white amorphous mass, no longer perfectly soluble in water. 
(Trommsdorff.) 

Urafums Valerate, — The solution of uranic valerate In excess of 
aqueous valerianic acid gives off a gas when exposed to the sun, and 
deposits uranous valerate in the form of a violet substance which, when 
dried in the air, is reconverted into a yellowish powder. (Bonaparte.) 

Uranic Valei'ote. — 1 At. valerate of silver dissolved in water is 
precipitated by 1 At. chloride of uranous oxide, and the filtrate left to 
evaporate in a place not exposed to sunshine. There then remains a 
yellow shining varnish, which gives off its acid at a gentle heat, and 
dissolves very readily in water, alcohol and ether. (Bonaparte.) 

Manganoui Valerate, — The solution obtained by heating manganous 
carbonate with ^he aqueous acid yields by spontaneous evaporation, highly 

VOL. XI. D 



34 AMYLENE: PRIMARY NUCLEUS om^o^ 

lustrous rheuibio tables, greasy to tbe touch jmd easily solnble in w^ier. 

(Trommsdorff.) 

Valei^ate of Bumuth, — The solution of nitrate of^bismuth is preci- 
pitated by valerate of eoda. (Righini^ J. Chim, mid. 22, 405.) 

Valerate of Zinc, — Zinc dissolves slowly in the aqueous acid. 
(Groto.) Sulphate of zinc mixed with valerate of soda yields the salt 
in laminsd. (Trommsdorff.) — Tbe dilute acid is saturated by continued 
boiling (best in a retort to avoid loss) with carbonate of zinc, filtered at 
the boiling heat, and the filtrate evaporated to the crystallising point. 
] ither the crystals which form each time the liquid cools are collected, or those which 
f m from time to time during gentle evaporation. In this case also Frederking recom- 
i;;^ih13 the use of a retort, because part of the acid volatilises. — White nacreous 

scales, like those of boracic acid, having rather an astringent than 
a sweet taste, permanent in the air (Trommsdorff); they redden litmus. 
(Wittstein.) They contain 29*5 p. c. zinc-oxide. (Wittstein.) They 
melt at 140° to a syrup, without loss of acid, and when ignited give 
off dense white vapours, which burn with a blue zinc-flame (Tromms- 
dorff), while oxide of zinc remains behind. (Wittstein.) Thev dis- 
solve in 5 pts. of cold, in 40 pts. of boiling water, in 14*4 pts. of cold, 
and in 16*7 pts. of boiling alcohol (Duclou); they dissolve in 160 pts. of 
cold water and in 60 pts. of cold 80 p. c. alcohol; these cold solutions 
become turbid when heated, and clear again on cooling; hence the solubi-. 
lity in water and alcohol diminishes as the temperature rises; on the 
other hand, the crystals dissolve in 500 pts. of cold and in 20 pts. of 
boiling ether. (Wittstein.) — Compare further: Grote, Bonaparte, Frederking 
(JV. Br. Aroh. 43, 2: Guillerraond & Ducloa {Rev, teienUf. 19, 70 & 71); Vutflart 
(N,J, Pharm. 6, 219). — The adulteration of this salt with butyrate of zinc, which 
closely resembles it, is noticed by Larocque & Uuraut, N. J, Pharm, 9, 430.) 

Valerate of Cadmium. — The aqueous acid slowly dissolves carbo- 
nate of cadmium, and yields, by evaporation, laminse resembling those of 
boracic acid, but having a still higher fatty lustre, and soluble in water 
and alcohol. (Bonaparte.) 

Valerate of Lead. — a, Trihadc. — The dry acid combines rapidlr 
and with great evolution of heat, with excess of finely-pounded lead- 
oxide, and on subsequently heating the product, it is found that 100 pts. 
of the acid have yielded 9 pts. of water. By exhausting the resulting 
mass with cold water, filtering from the lead-oxide which remains free, 
and evaporating the filtrate in vacuo over oil of vitriol, delicate, shining 
needles are obtained, united in hemispherical masses, infusible, and 
fmielling slightly of valerianic acid. They absorb carbonic acid from the 
air, and dissolve sparingly in water. (Chevreul.) 

h. Monobasic. — When the solution of lead-oxide in excess of aqueous 
valerianic acid is evaporated, with frequent addition of acid, so as to keep 
the acid in excess, the salt remains as a fusible amorphous residue; but by 
evaporation in vacuo over oil of vitriol, it is obtained in shining flexible 
lamiufe. (Chevreul.) By quickly evaporating the solution to a syrup 
and cooling, a mass is obtained having the consistence of turpentine and 
capable of being drawn out into threads; by slow evaporation the salt is 
obtained in laminated crystals. (Grote.) The carbonate of lead dissolves 
slowly, and there is obtained a very sweet uud afterwards astringent- 
tasting liquid, yielding, by quick evaporation, a viscid mass, and by 



VALERIANIC ACID. ^5 

flower evaporatiou, white laminie, both- of which dissolve -very -readily ia 
water, (TrommsdoriT.) 

7)riba$iCt anltydrout, Chevreul, 

SPbO « 336 .... r8-a2 78 

CWH»03 93 .... 21'68 



. . 2 PbO,CWH»PbO< „ 429 .... 10000 

MonQbaiiCf lanUna, Chevreal. 

PbO 112 .... 54*04 6V5 

C^H^Cfi , 9 3 .... 46-36 

CWH»PbO< 205 „.. 10000 

. Ferrou$ Valerate. — Iron filings immersed in the aqneous acid slowly 
eliminate hydrogen, and form a black-brown coagplum naying a sweetish 
astringent taste. (Trantwein.) ^ 

Ferric Valerate, — a. Monxhocidl — Obtained by heating 6 to J 00°,' 
as long as it continues to lose weight. Brown powder. (Wittstein.) 

5. BirQ^idJ — An aqueous solution of scsquichloride of iron is pr$^ 
cipitated by valerate of sodd, free valerianic acid then remaining in the 
liquid; and the nrecipitnte is washed with a small quantity of water and 
dried below 20 . Dark brick-red amorphous powder having somewhat 
of the smell snd taste of valerian. By exposure to a slowly increasing 
heat, it gives off all its acid without melting; but when quickly heated, 
it melts, and gives off <]ense inOammnble vapours, having scarcely any 
odour of valerianic acid but smelling rather like butyric acid. Gives off 
aU its acid to boiling water, leaving pure ferric hydrate. Dissolves readily 
in hydrochloric acid. (Wittstein.) 

Salt a dried at \W. Wittsteiii. 

. F^O» BO 43-95 4.17* 

C»H«0« 93 .... 51*10 68-12 

HO 9 .... 4'95 5-17 



Fe»03,CWH»0< 182 .... 10000 lOOOO 



-^- 



Salt h dried at 20"* Wittstein. 

Pe»0» 80 .... 28'17 26-85 

S C«>H»0» 186 .... ^5-50 69-2'^ 

2 HO 18 .... 6-33 3-93 

Fe203,2CWU»0* 284 .... lOO'OO lOO'OO 

The ralculation does not qrite agree with the analysis, and accordingly WSttftein 
prefers more complicated formalie; but his method of estimating the anbydrooa acid and 
the water cannot lead to aocarate resnltj. 

. c. Wiih excess of acid f — By immersing iron wire for some time in the 
aoid, and boiling the resulting dark red mass with water, a solution is 
obtained, en which however the greater portion of the product floats in 
the form of a dark red-brown oil. [salt b ?] The solution gives a brow^ 
pteeipitate with potash. (Trommsdorff.) 

Valerate of Cobalt —Hhe rose-coloured solution of carbonate of cobalt 
in warm dilute Talorinnic acid becomes covered with a red film when 

D 2 



36 AMTLBNE: PRIMARY NUCLEUS CWH» 

evaporated, and dries up to a violet-red translucent mass. When tlie 
solution of this mafia in water is evaporated to a syrup and set aside in 
the cold, yiolet*red, transparent prisms are produced, having a sweet, 
slightly astringent taste, permanent in the air, and easily soluble in 
water and alcohol. . (Trommsdorff.) 

ValemU of Nickel. ^CMhouoXe of nickel dissolves with difficulty in 
the heated aqueous acid, whereas with the dry acid, it quickly forms a 
green oil. This oil dissolves very sparingly in water, forming a very 
pale green solution; but with alcohol it forms a pale green solution which, 
on evaporation, deposits a pale green powder, sparingly soluble in water. 
(Trommsdorff.) 

Cvpric Valerate, — The dry acid exposed to the air in contact with 
cupric oxide assumes a dark ffreen colour in the course of some weeks; the 
hot aqueous acid forms with cupric carbonate a bluish green solution, 
which, on evaporation, yields green prisms permanent in the air, easily 
soluble in water and also in alcohol. (Trommsdorff.) [For the crystalline 
form see Schabup, Jahresber, vn, 442.] On adding the concentrated acid to 
aqueous cupric acetate, nothing appears at first; but on agitation, greenish 
oil-drops are produced, consisting of cupric valerate, which after 5 to 
20 minutes, takes up water and changes to a green-blue crystalline powder. 
Valerianic acid mixed with butyric acid produces, when stirred up with a 
slight excess of cupric acetate, at first the greeu oil-drops, on which, as 
well as on the glass rod, there are dcpositea, after a while and without 
further turbidity, the pale blue scales of cupric butyrate. (Larocquc &c 
Huraut, iV. J, Fhaim, 9, 430.) 

Mercurous Valerate, — The boiling thickened acid dissolves a small 
quantity of mercurous oxide, and yields small needles on cooling. 
(Grote.) 

Mercuric Valerate, — Mercuric oxide dissolves in the heated oily acid, 
forming an oil which on cooling solidifies in a mass having the con- 
sistence of plaster; this mass is insoluble in cold, but soluble in hot 
water; the colourless solution deposits slender white needles on cooling, 
and the mother-liquor leaves on evaporation, a red mass insoluble in 
water and dissolving with red colour in the dry acid. The white slender 
needles which are likewise deposited on mixing valerate of potash with 
mercuric nitrate or chloride, are converted by moderate heating into a 
red basic salt, with loss of acid. (Trommsdorff.) 

a 

Valerate of Silver, — A solution of nitrate of silver is precipitated by 
a slight excess of an alkaline valerate. The precipitate, which is curdy 
at first, becomes crystalline after immersion for some time in the liquid 
(fittling), and then resembles fulminating silver (Dumas & Stas); 
appears to consist of lamin® soft to the touch and having a silky lustre. 
(VVinkler.) On evaporating the aqueous solution, the salt is obtained in 
white lamin» having a metallic lustre. (Ettling.) The salt blackens 
quickly in the light (but less quickly than acetate of silver according to 
Winckler) and must therefore be dried in the dark. (Dumas Sk, Stas.) 
When heated, it emits vapours having the odour of valerian, then melts 
into a black mass, which suddenly emits extremely offensive vapours, 
and leaves pure white silver. (Winckler.) 



ANHYDROUS VALERlANtC ACID« 37 

Ai 130°. EtUmg. Moro. ^g^ * Winckler. 

10 C 60 .... 28*71 28-65 .... 28-3 

9 H 9 .... 4-31 4-33 .... 4*3 

Ag 108 .... 51-67 51-93 .... 51-64 .... 516 .... 5294 

4 O 32 .... 15-31 15-38 .... 158 



CWH»AgO* 209 .... 10000 100-00 .... 10000 

EttUng & Winckler examined the salt from valerian ; .Moro that from the bvk of 
Vt^mum Opuluaj and Domas & Stas, that obtained from fusel-oil. 

Concentrated valerianic acid mixes in all proportions with alcohol 
and ether. (Chevreul, Grote^ Damas & Sbas.) The solution in an equal 
quantity of absolute alcohol is rendered by a small quantity of water; 
and clear again by a larger quantity. (Trommsdorff.) 

It dissolves abundantly in strong acetic acid of sp.gr. 1-07. (Tromms- 
dorff.) 

According to Trautwein^ it mixes with oil of turpenline in all propor- 
tions; according to Grote, on the other hand, only partially (perhaps 
from containing water %), and according to Trommsdorff^ not. at all; 
neither with olive-oil. . . 

It dissolves common camphor, (Trommsdorff^ Trautwein.) 

It dissolves a few resins. (Trautwein.) 



f . Anhydrous Valerianic Acid« 

C^^HW or C»H^W = c'oh^o*}^' 

Cbiozza. CompU rend,- 35, 568; Ann. Fharm. 84, 106; J, pr, Chem. 
58, 23; Chem.Gaz. 1853, 52; Jahresber. 1852, 453. 

Valerie Valerate, Valeric Anhydride, 

Prepared by the action of 1 pt. oxychloride of phosphorus on 6 pts. 
valerate of potash (obtained in a state of' purity by evaporating the 
alcoholio solution and melting the residue); the product, a thick oil, 
yields, when treated with a very dilute solution of carbonate of sgda, and 
then with ether, an ethereal solution which leaves the anhydrous acid 
when evaporated. 

Colourless, tolerably mobile oil, lighter than water. Boils without 
decomposition at about 21 5^ When recently prepared, it has a faint and 
rather unpleasant odour; when rubbed between the hands, it imparts to 
them a persistent odour of ordinary valerianic acid. Its vapour attacks 
the eyes and excites coughing. By boiling water it is converted slowly, 
and. by alkalies quickly, into ordinary valerianic acid. With aniline 
it forms valeranilide C«NH"0'. (Chiosza.) f . 



in amtlrhb; primart nucleus c»h«». 

Sulphide of AmyL 

Balard. JV. Ann, Chim, Phys.' 12, 294; also J. pr. Chem, 94, 132. 

••. t> ... ... 

Schwrfelamyl, Schforfelmylafer^ Ether sulfhydramylique. 

Chloride of amyl ia distilled with an alcoholic solution of mono- 
sulphide of potassium — or better, the mixture, enclosed in a sealed 
^lass tube is heated for some time [to 100° 1J; the liquid then decanted 
from the chloride of potassium, and the sulphide of amyl separated from 
it by addition of water. 

Colourless liquid, boiling at 21 6^ having a ^'apour-density of 6*3 and 
a strong odour and iast* of onions. (Balard.) 

BalanL 

WC ; 60 ;... C8'97 68-25 

il H 11 .... 12-64 12-65 

S 16 .... 18-39 19-10 

CMH»S 87 .... 100-00 100-00 

* 

Voh Density. 

C-vapoar \ ;. 10 .... 4-1600 

H-gM 11 .... 0-7623 

S-yapour \ .... 1-1093 

Vapour of CioH"S 1 .... 60316 

[According to tbii, tile rifpon^ of fttlphicle of amyl if ni(matomic> like that of 
sulphide of ethyl (viii, 338). the atomic weight of these bodies, as well as that of 
the corresponding ethers, ought perhaps therefore to be doubled.] 



y 



Amylic Meroaptan. 

Krutzsch. J. pr, Chem, 31, 1. 

Balard. JV. Ann, Ghim, Fliys, 12, 294; also J. pr. Chem, 34, 133. 

^RDMANN & GERATfiEwonL. J. pr, Chem. 34, 447. 

Amyi-mereapatan, Mfylernercapatam Amyl8ubiir»8chwtfeluja99Sr»tqf, Mertt^iak 
ianylifuft 

Prepardtion. 1. Purified fusel-oil is mixed, gradually and with 
agitation, with an equal weight of oil of yitriol; the mixture neutralised 
with aqueous carbonate of potash; the sulphamylate of potash whick 
remains in solution filtered from the sulphate of potash; and the filtrate 
mixed with caustic potash, saturated with sulphuretted hydrogen, and 
distilled in the chloride of calcium bath in a capacious retort with a cooled 
receiver. The oily drops which float on the surface of the waterlr dis-. 
till ate are then removed with a pipettd, set aside over chloride of calcium, 
and rectified after decantation. (Krutzsch.) 

CJ0H"KO2,2SO3 + KS,US « Om^^& + 2 (K0,S03). 

When crude fusel-oil is used, a brown oil rises to the surface on the 
addition of the potash; and even if this be taken away, and then dis- 
tilled after saturation with sulphuretted hydrogen, the resulting mer- 



AMYUC MBKCAPTAN. 3© 

captan is still impure. (Erdmann & Gerathewohl.) — 2. Sulphamylate of 
lime is distilled with hydrosulpbate of potassium. — 3. Chloride of amjl is 
distilled with an alcoholio solution of hydrosulphate of potassium •— or 
better, the two substances are heated together in a sealed tube, and the 
amylic mercaptan separated as an oil rising to the surface bj addition of 
water. (Balard.) 

C'0H»C1 + KS,HS - CWH«S2 + KCl. 

Properties. Colourless oil, of great refracting power, and sp. gr. 
0-835 at 21°. (Krutzsch.) Boils at 117° (Krutzsch), at 117 to 118- 
(Erdmann A Gerathewohl), at 125^ (Balard.) Vapour-density = 3*631 
(Krutzoh), 3*9. (Balard.) Has a pungent allipceous odour (Krutzsch), 
much more disagreeable than sulphide of ethyl, like that of sulphuretted 
hydrogen. (Balard.) 

Krutzsch. Balard. 

IOC 60 .... 57-69 57-29 .... 58-25 

12 H 12 .... 11-54 11-36 .... 11-60 

2 S 32 .... 30-77 30*55 .... 

C?OH»S« 104 .... 100-00 99-20 

C.TBpoiir 10 .... 4-1600 

H-gas 12 .... 0-8316 

S-vapour ^ .... 2-2186 

' - • . .. . . 

Merc-vapoar 2 .... 7-2102 

1 .... 3-6051 

Deconipodtions, 1. When kept in loosely closed bottles, it gives ofl 
sulphuretted hydrogen, and is converted into sulphide of amyl. (Balard.) 
' — 2, On cold nitric acid of sp. gr. 2-25, amylic mercaptan floats at first 
almost unaltered; but on long standing or gentle heating, it turus red, 
then quickly becomes very hot and gives off nitrous fumes, and ulti- 
mately forms two layers, the lower of which contains nitric acid, amylo- 
sulphurous and a small quantity of sulphuric acid, while the upper is a 
variable oily mixture, sometimes lighter, sometimes heavier than water. 
A sample of this oil lighter than water containit 5602 p.c. C, 10*38 H, 9'24 S and 
24*36 O. (Erdmann and Gerathewohl.) 

KmyWa mercaptan combines with lead-oxide^ forming a yellow flocculent 
mass, and when added to the acetate, throws down a coagulum of the 
consistence of turpentine. (Krutzsch.) 

It does not act on cupric oxide, but throws down from the sulphate a 
greenish glutinous mass. (Krutzsch.) 

With mercuric: oxide it combines, with violent evolution of heat, 
forming a colourless liquid, which, on cooling, solidifies in a translucent 
lamino -radiated mass, which melts again at 100^ is not decomposed by 
boiling potash-ley, is not soluble in water, and but sparingly soluble iu 
boiling alcohol and ether, whence it separates for the most part iu scales 
on cooling. (Krutzsch.) Insoluble in water and alcohol, but soluble in 
ether. (Balard.) Its powder mixed with pounded glass and ffently heated 
in a retort, yields, when sulphuretted hydrogen is passed through it, 
amylic mercaptam, which may be purified from adlioring sulphuretted 
hydrogen by repeated rectification. But by decomposing with aqueous 
hydrochloric acid, only a small quantity of amylic mercaptan is reco- 
rered. (Erdmann & Gerathewohl.) 

The compound with silver-oxide resembles mercaptide of silver, and 
18 insoluble in water -^nd alcohol, but soluble in ether. (Balard.) 



40 AMYJ,E>*J:2 PBIMARY NUCtCtS C^'U" 



Bisulphide of Amyl P C"H"3« « 

0. Henry (1849). X. Ann. Chim. Pht/a. 25, 246; also Compt rend. 
28, 48; also If. J. Fharm, 14, 247; also J. pr. Cliem. 40, ICO. 

DoppeltKhvrfelamylf Bitulfnre d'Amyle. 

Crystalline araylosnlphate of potash and a highly concentrated solu- 
tion of bisalphide of potassiam in about equal volumes, are distilled 
together in a retort of four times the capacity of the mixture, on account 
of the strong intumescence; and the yellowish oil which floats on the 
watery distillate is rectified two or three times over chloride of calcium. 

The product is a pale yellow distillate, which boils at 210^ to 240% 
has a strong penetrating odour, — and another distillate of a flne yellow 
colour, which boils between 240° and 260°, has a specific gravity of Of^ 18 
at 19°; and the same odour. 

Henry. 

IOC 60 .... 58-25 58-30 

11 H 11 .... 10-68 10-42 

2 S 32 .... 31-07 

C>*H"S« 103 .... 100-00 

[Perhaps only a mizture of C^^^H^^ss and Ci^^H'oS', a view which is confirmed by 
the rise of the boiling-point.] 

Henry does not state the boiling-point of the sample which he analysed. 

The oil, when decomposed by nitric acid,yields Erdmann and Gerathe- 
wohla sulphamylosulphuric acici] (p. 52). (Henry.) 



Iodide of Amyl. 

C'«H"I = C*«H",HL 

Cahours (1839). Ann. Chim. Phy9. 70, 81 i also Ann. Fhaitn. 

30, 297. 
Fbamklamd. Ann, Pha)-m. 74, 42* 

lodamylj lodtnylqfer, iodwtuferttqfuaures Amylen, Hydriodate d'Amyiene. 

^ Preparation. 1. Fifteen pts. of fusel-oil are distilled at a gentle heat 
with 1 pt. of phosphorus and 8 pts. of iodine, and the distillate repeatedly 
washed with water, digested with chloride of calcium, and rectified two or 
three times. (Cahours.) — 2. Four pts, of iodine are gradually dissolved 
in 7 pts. of pure fusel-oil, and a stick of phosphorus moyed about in the 
liquid after each fresh addition of iodine, till it is completely decolorised; 
the oil, which gives off fumes of hydriodic acid in the air, distilled in the 
water-bath, till a thick, non-volatile, very acid liquid, insoluble in water, 
remains; the distillate, containing hydriodic acid and unaltered fusel-oil, 
washed with water, set aside for 24 hours over chloride of calcium, and 
rectified; and the last third, which passes over at 146^ collected as pure 
iodide of amyl. If the hydriodic acid has not been completely removed 
by the washing, the distiPate is violet, but becomes colourless by reotifi- 



lOmDE OF AMYL, 41 

cation over mercury. — The first two-thirds, which pass over botweon 
120° and 146°, consist of impure iodide of amyl, and must be again 
treated with iodine and phosphorus. (Frankland.) — Grimm (Ann, 
Pliarm. 92, 383) adds 10 oz. of iodine and a small quantity of phos^ 
phorus to 8 oz. of pure amy lie alcohol. The amy lie alcohol is mixed 
with 4 or 5 per cent, of water, and saturated with iodine; the solution, 
after being heated to 50% shaken up with a sma)! quantity (about \ of an 
ounce) of phosphorus till it is decolorised; again saturated with iodine 
and treated with phosphorus, and so on till the assigned quantity of 
iodine has been used: the liquid must be well cooled, as often as any rise 
of temperature takes place. The strongly fuming liquid ultimately 
obtained is distilled after standing for 24 hours; the distillate shaken up 
with water; iodine added in small quantities as Ions as its colour 
disappears; and the heavy liquid at the bottom re-distilled as before with 
water> then left to stand for a few days, and rectified. 

Fropertiei, Colourless liquid, heavier than water, boiling at 120% 
under a, pressure of 076 met.; of Yapour<-density 6*675; having an 
alliaceous odour and pungent taste. (Cahours.) Sp. gr. 1*511 ^t 11*5°; 
1-4.936 at 20° (Or imm); boiling point 146° at 0*75 met. pressure; 140° 
(Grimm.) Has a faint ethereal odour and sharp biting taste. (Frankland.) 

Cfthoura. Fraukland. Grimm. 

IOC..., 60 .... 30-46 .... 31-00 .... 30*32 .... 305 

11 H 11 .... 5-58 .... 5-29 .... 5-55 .... 5-89 

1 126 .... 63-96 64*10 to 62-61 

cm"! 197 .... 100-00 

Vol. Density. 

C-vapour 10 .... 4-1600 

H-gM 11 .... 0-7623 

I-vapour I 8-7356 



Yap. of C»OH"I 2 .... 13-6579 

1 .... 6-8289 

Decompositions^ 1. Iodide of amyl is not inflammable when cold, but 
when heated to its boiling point, may be set on fire by a flaming body, 
and bums with a purple flame. (Cahours.) — 2. It unc^rgoes no change 
in ordinary day- light, but in sun-shine acquires a continually deepening 
yellow colour from separation of iodine; it may be rendered colourless 
again by potash. (Cahours.) It is but slowly decomposed by aqueous 
potash, even at a boiling heat, but quickly by alcoholic potash, so that 
iodide of potassium separates out on cooling. (Cahours.) — 4. Heated 
with zinc-amalgam in a sealed glass-tube^ somewhat above its boiling 
point, it is resolved into C*H» [C^H^^ amylene], C»H«, rC»°H», hydride of 
amylj, C"H" [C^R^] and iodide of zinc; the compound C»«H"Zn ia 
likewise formed (Frankland); 

[4CWH"I + 4 Zn « C^HW + C^H^ + C-^Ra + 4ZnI ; 
and : 

C»H"I +2Zn « CMH^Zn + Znl.] 

Pure zino does not decompose iodide of amyl till heated to 190^, and then 
but slowly; potassium decomposes it very easily, even at its meltiqg point, 
with formation of the same products, but not of C*^11"K. (Frankland.) 



42 AMYLENE ! PRIMARY NUCLEUS OHw 

— In presence of water, rinc decomposes iodide of amyl, even at 14^**, 
and more <j[uiokly, into C»H« [C*^H»] and oxyiodide of «nc. (Frankland); 

[CWH"1 + HO + 2Zn - CMII»»ZnT,ZuO]. 



Bromide of Amyl. 

Cahoubs (1839). Ann. Ckim. Pfiys, 70, 81j also /. pr, Chem, 17, 224. 
Bromamylt bromwoMerstoffaaurei Amylen, Bromhydraie d*Amylene. 

Obtained by distilling fusel-oil with phosphorus aqd bromine, similarly 
to the iodide. 

Transparent, colourless; heavier than water; distils without decom- 
position; nas an alliaceous and pungent odour and a sharp taste : 

Cahonra* 

IOC 60 .... 39-74 4179 

11 H 11 .... 7-28 7-55 

Br 80 .... 52-98 

C«»H»Br.. » 151 .... 10000 

Vol, Density. 

C-rapour 10 .... 41600 

H-ga« 11 .... 0-7623 

Br-vapour..... 1 .... 5-5465 , 

Vap. of C»oH"Br 2 .... 10*4688 

5*2344 

Bromide of amyl is difficult to set on fire by a flaming body, and 
burns with a greenish flame. It is decomposed slowly by aqueous, 
quickly by alcoholic potash, with formation of bromide of potassium. It 
is not altered by exposure to sunshine. Dissolves in alcohol and ether. 
(Cahonrs.) 



Chloride of Amyl. 

C'°H"C1 = C^^H^KCl. 

Cahours (1840). Ann. Chim. Phys, 75, 193. 

Balard. N. Ann. Chim. Phys. 12, 294; also J, pr, Chem. 34, 128. 

Chloramgl, Cklormylqfer, Ether hydrochloramyliquey Chlorhydrate d*Amyline. 

Preparatwn. 1. Fusel-oil is distilled with an equal weight of penta- 
chloride of phosphorus, and the distillate repeatedly washed with water 
containing potash, dried over chloride of calcium, and finally rectified in 
a bath of fioJt-solution. (Cahours.) — 2. Fusel-oil is distilled with strong 
liydrocbforic acid^ with fre<|aent cohobaiion; the resulting cMoride of 



CHLORAMTLAL. 43 

amjl pipetted from the acid distillate; and freed from nnaliere^i faeel-oil 
by waeliing with strong hydrochloric acid. (Balard.)— -3. Fusel oil is 
tettirated in a tabulated retort with hydrochloric acid gas, whereupon ll 
becomes heated and turns gfeen; it is then distilled, the passage of the gas 
bein^ continued all the while ; and the amethyst-coloured distillate of 
chloride of amirl is Washed with water and carbonate of soda^ afterwards 
dried over chloride of oalcium, and rectified.' (Rieckher. Jahrb. pri 

Ptoperties^ — * Colotrr less liquid, boiling at 1 02"" (Cahours), between 1 00® 
and 101^ according to Balard. Vapour^'density 3*805. (Balard.) Has- a 
tolerably pleasant aromatic odour; neutral; does not render silver- 
solution turbid. (Cahours.) 



10 c* ,.. 


■ : ■; 


600- .... 56-39 
11 .... 10-34 
33-4 .... 33-27 


• ••• 

• ••< 

• > • 


• ••« 


Cahoun. 
56-06 .... 
10-43 .... 
33-44 .... 


Balard. 
55-9 


11 H ... 


( ... 


10-3 


CI ... 




33*5 








C'»H»C1 


• 

C-vaponr ... 

H-gas 

Cl.ffaa 


106-4 .... 100-00 


roi. 

10 

11 
1 


• •■■ 

• ••• 

• «■ • 


99-93 .... 

Density. • 
4-1600 
0-7623 
2-4543 


99-7 


















Vapour of C«H"C1 


2 

1 


• ••• 


7-3766 
3-6883 





Chloride of amyl bums with a green-bordered flame, giving off 
* hydrochloric acid. (Cahours.) — Exposed to the sun in a bottle filled 
with dry chlorine gas, it is converted, first with quick and afterwards with 
decreasing evolution of hydrochloric acid, into C^^H*C1', a colourless 
liquid) which smells strongly of camphor^ and would probably be com- 
pletely converted into C*^CP^ if the action of the chlorine were longer 
continued. (Cahonrs.) — ^ Heated to 100^ in a sealed tube with alcoholic 
potash or with monoenlphide of potassium, it is resolved into amylic 
ether and chloride of potassium, or into sulphide of amyl and chloride of 

polassiitm*' (Balard.) 

C«»H"CI + KO - C"H"0 + Ka 

and C>»H"Cl + K8 * C'H^'S + KCL 

Alcoholic potash and monosulphide of potassium do not act upon it in tho 
cold. — When chloride of amyl is distilled with potash-lime, amylen# 
dbtils over. (Balard.) 

Chloride of amyl is insoluble in water. (Cahours.) 



ChloramylaL 

Cahours. Ann. Chim, Phyn. 70, 81; also Ann, Phamu 30, 209. 

When chlorine gas is passed through about 30 grammes of fusel-oil, 
absorption takes place at firsts with formation of a large quantity of 
hydrochloric acid, the liquid turning brown and becoming heated to 
ebullition, so that it becomes necessary to cool it from without; but- 



44 AMYLENE : FRIMARY NUCLEUS cm^* 

afterwardtj tho action becomes slew, and mast be sastaineil by g^ntlo 
heating, till the chlorine ceases to act. The resulting brown oil is 
repeatedly washed with water containing carbonate of soda, then 
digested over chloride of calcium, and rectified two or three times. 

In this manner, a }>ale yellow oil is obtained, hearier than water, and 
boiling at about 180°; its vapour excites coughing when inhaled; it ia 
Mfcsteless at first, but leaves a very pungent after-taste. 

The recently prepared alcoholic solution does not precipitate nitrate 
of silver, but on standing it turns acid and precipitates the silver. 

Chloramylal is insoluble in water and in alkaline liquids, but dissolves 
in alcohol and ether. (Cahours.) 

10 c 

HCl 

8i H 

2 O 







Choars. 


60-0 


.... 43-60 


....•••I 44*^v 


531 


.... oo*d9 


38-38 


8-5 


.... 6-18 


605 


160 


... n-63 


11-34 



137-6 .... 100-00 100-00 

. • • ■ . • • 

Probably the action oi the chlorine was not complete. (Cahours.) [Perhaps 
therefore C'*CPH«.0*J. 



T. TeUuramyl. C^oH^Te. 

F. WoHLER & J. Dean. Ann, Fharm. 97, 1. 

Obtained in an impure state by distilling telluride of potassium with 
a solution of amylosulphate of lime (prepared with amylic alcohol which 
passed over at 132° in the distillation of crude fusel-oil). As soon as the 
mixture began to boil, a reddish yellow liquid passed over with the water 
and sank to the bottom of it. The receiver was changed when the liquid 
which passed over began to exhibit a light colour; and at last colourless 
amylic alcohol distilled over. 

The liquid thus obtained has an odour like that of tellurethyl and 
telluromethyl, but less strong and disagreeable. Exposed for some time 
to tho air, it is converted into a white mass. The boiling point wa& found 
to be 19S°; this determinatioo is however quite uncertain, because the 
compound decomposes when heated, even in an atmosphere of carboni<). 
acid, gradually depositing tellurium iu small shining prisms. 

WShler & Dean. 

IOC 60 .... 44-4 .39-5 .... 38-3 

11 H 11 .... 8-1 7-4 .... 8-2 

Te 64 .... 47-5 370 .... 35-4 

CioH"Tc 135 .... 100-0 83-9 .... 81*9 

The great differences between tbe analytical and calculated results are probably doe 
to tbe presence of amylic alcohol separated by the decomposition above noticed. To 
remove this source of error, the body had been dissolved in warm weak nitric acid and 
teprecipitated with sulphite of ammonia ; but this mode of purification was evidently 
ineffectusl. The carbon and hydrogen found by analysis agree nearly wiUi the formula 
of tellurobutyl C^UrTe, which requires 39*6 p.c. C, 7'4 H, and 53*0 Te; but the 
amount of tellurium obtained is much too small. 



CARnONATE OF AMYL. 45 

Nitrate af Telluramyl, — Telluramyl Lc&ted with modorately strong 
nitric acid, is converted, with evolution of nitric oxide gas, into a 
transparent, colourless, heavy oil, which appears to be the nitrate in the 
amorphous state. It dissolves in a large quantity of boiling water, and if 
the quantity of water has been rightly chosen, separates after a few days 
in thin rhombic tabular crystals. If the solution is too concentrated, it 
becomes milky on cooling, in consequence either of the salt again 
separating in the oily form, or else of another body separating out, in 
which the crystallisable salt remains dissolved. — Nitrate of telluramyl is 
permanent in the air, inodorous, and melts at 40"^. When heated in tho 
air, it bums with a blue tellurium-flame. Sulphurous acid throws down 
from its solution a yellowish red liquid having an offensive odour. 

The nitrate gave by analysis 37*8 p. c. tellariuin. The formula C^^^H^TeO.NO^ 
reqoires 32*0 p. c. If the composition of the salt were analogous to that of the sulphate 
and oxalate of tellurethyl (viii, 385), viz., CWH»TeO,HO + C">H»TeO,NO», the 
amonnt of tellurium would be 36*9 p. c« The formula of nitrate of teUurobutyl 
requires 35 p. c. tellurium. 

Chloride of Telluramyl is formed by mixing the solution of the nitrate 
with hydrochloric acid or chloride of sodium. Colourless, viscid, glutinous 
inodorous oil, heavier than water. 

The Bromide is obtained in a similar manner, and is a pale-yellow 
heavy oil possessing similar properties. 

The Iodide separates from the milky liquid at first produced, in the 
form of heavy, dark yellowish red, semifluid drops; it could not be obtained 
in the crystalline form. When boiled with alcohol, it was converted into 
a pale yellow, amorphous, inodorous powder, which, when treated with 
ammonia, acquired a vermilion colour, dissolved in the ammonia when 
heated, and separated out again with the vermilion colour on cooling. 
Nitric acid separated iodine from it. 

Oxide of Telluramyl was obtained by digesting the chloride with 
silver-oxide and water: the viscid character of the chloride renders the 
decomposition very slow. The oxide is soluble in water, and so strongly 
alkaline, that it separates ammonia from sal-ammoniac. With hydrochloric 
acid it reproduces the oily chloride. Sulphurous acid reduces telluramyl 
from it in yellowish red, odorous, oily drops. — Ou neutralising the oxide 
with sulphuric acid, and evaporating the solution, it yielded^ at a certain 
degree of concentration, colourless, viscid drops, which, after cooliug 
gradually changed to groups of small prisms. (Wohler k Dean.) %, 



Conjugated Compounds of tlie Primary Nucleus C*"H". 

Carbonate of Amyl. 

Medlock (1849). Chem. SoC, Qu. J. 1, 363. Ann, Pkarm. QO, 217. 
Koklemauret Amylojpyd, Kohlenmy tester . 

In the distillation of chloroformiate of amyl (p. GO), after carbonic 
and hydrochloric acid have gono ofl*, and the boiling point has risen to 



46 AMYLENB; PRIMARY sNUCLEU^ C*OHU>. 

224° and become staiionary there^ parbonate of amjl passes over, and 
must be purified by further rectification. 

Transparent liquid of sp. gr. 0'9H4j boiling steadily at 224"", and 
having a not unpleasant odour, 

Medlock. 

II C 65 .... 65-35 G5-19 

11 H 11 .... 10-89 10-9-1 

3 O 24 .... 23-76 23'87 

C"H"Os 101 .... 10000 lOOOO 

Carbonate of amyl is immediately decompoaed by alcoholio potash, 
into auiylic alcohol and carbonate of potash, whioh produces a thickening 
of the liquid. — With aqueous or alcoholic potash it does not form sny oompound of 
the nature of urethane* (Medlock. ) 



Terbasic Borate of Amyl. 

C«>H»BO* = 3C"H"0,B0'. 

Ebblmen & Bouquet (1846). iV. Ann. Ohim. Ph'js. 17, Gl) also «/. pr 
Cheni, 38, 219. 

Triboraie qf Amyl, Drittellfortaures Amyloxydf Driitel-Bormyhtier, ProtoboraU 
antique. 

Preparation, A mixture of chloride of boron and carbonic oxide is 
passed (as in the preparation of terbasic borate of ethyl, viii, 894), 
through fusel-oil, till hydrochloric acid begins to escape, and an oil rises 
to the top of the liquid saturated with hydrochloric acid; this oil is then 
decanted and rectified, the portion which distils over between 260^ und- 
280° being collected apart and rectified again. 

Properties, Colourless oil, of sp. gr. 0*870 at 0^. Boils between 270** 
and 275^ and has a vapour-deusity of 10*55. Has a faint odonr of 
fusel-oil. 

Ebelmen & 
Bouqaet. 

30 C 180-0 .... 66-22 65-0 

33 H .330 .... 12-U 12-3 

o Kj M....C ••• 24*0 .... o*o3 

B0» ..., 3-4-8 .... 12-81 11-9 

CaoH3ao3,BOa 271-8 .... 100-00 

Vol, Dcn«i£y. ' ^' 

C-vapour ' 30 .... 124800 

H-gas « ^.. 33 ,.., 2-2869 

B-vapour...i 1 ;.,. 0-7487 

O-gas a ,... j 3-3279 

Vapour 2 .... 18-8435 

1 ..« 9-4217 '> 

This compound burns with a white green-edged flame, giving off 
vapours of boracic acid. — In contact with water, it is converted into 
boracic acid and fusel-oil. (Ebelmen & Bouquet.) 



PHOSPHITE OF AMYl.. 47 

• -• -. ... 

Biborate of Amyl. 

CioHiiBH)^ = C^°H"0,2B0». 

Ebblmen (1846). N. Arm. Chim. Phy$. X6, 139; also Ann, Pharm, 57 
829; .idsov. pr, Chem. 37, S55, 

Zwer/kehborsaureg Ameloxyd, Doppelt-BormyUster, Deutoborate amylique. 

Formation and Preparation. On mixing 2 pts. of fusel-oil with 1 pt. 
of Titrefied boraeic acid in powdor^ a slight evolution of heat takes place, 
and the mixture yields scarcely any distillate at 180°, but if afterwards 
treated with anhydrous ethcr^ gives up to it the borate of amyl, which 
remains behind on evaporating the filtrate, ultimately between 250° 
and 270°. 

Properties. Like biborate. of ethyl, yellowish, transparent; at 20°, it 
may be drawn out into long threads, like softened glass. Smells like 
fusel-oil and has a burning taste. 

Ebelmen. 

IOC fiO-0 .... 40-38 39*1 

IIH no .... 7-40 7-3 

8-0 .... 5-38 8-C 

2 BOg 69-6 .... 46-84 45 

CiWO,aBO» 148-6 .... 10000 1000 

Biborate o£ ethyl remains unaltered up to 300°; above 300°, it gives 
off white fumes in the air, then swells up and leaves fused boraeic aeid. — -> 
It bums with a green flame. — It is decomposed by water, and even by 
damp air, into boracio acid and fusel-oil. (Ebelmen.) 



Phosphite of Amyl. 

C«>H»PO« = 2CWH^^0,PH0*. 

WuRTZ (1845). N. Ann. Chim. Pht/$. 16, 221; alsp Ann. Pharm. 58, 75; 
abstr. Compt. rend, 21, 358. 

Phosphorig-Myle9terf'Amylpho»p7ior»aure9 Amyloryd, Ether amylophoaphoreux. 

Formation, (p 15). •'^Preparation, '1 voL terohloride'of phosphorus 
is slowly dropped into 1 vol. fusel-oil, and a small quantity of water. very 
slowly added, the vessel being well cooled, so that the product may not 
become coloured by the temperature rising too high. After all the 
Qxcess of chloride of phosphorus ba« been decomposed by the water, the 
mixtnre is shaken up with an equal volume of water; the oily mixture 
of phosphite of amyl and amylophosphorous acid, which rises to the 
surface on leaving the liquid at rest, decanted; freed from hydrochloric 
acid by repeated washing with water, and from amylophosphorous acid by 
washing with dilate carbonate of soda, till the residual phosphite of amyl 
no longer reddens litmus; then washed twice with water; and heated 
several times in vacuo to 80° — 100° to drive off water and chloride of 
amyl. Should the phosphite of amyl be coloured, it must be rectified in 



48 AMYLBNB: PRIMARY NUCLEUS C^H^. 

vacao; bnt tliis process is alvrays attended with a certain ainoant of 
decomposition; for the distillate contains fueel-oil^ and an acid residae 
is left. 

Properties, Colourless or pale yellow oil, of sp. gr. 0-9G7 at \0\ 
Boils only at a high temperature and with some decomposition. Smella 
slightly of fusel-oil; has a very pungent and disagreeable taste. 

Wartz. 

20 C 120 .... 53 96 5427 

23 H 230 .... 10-34 10-38 

P 31-4 .... 1412 12-55 

6 480 .... 21-58 22-80 

et)Hsspo« 222-4 .... 100-00 10000 

From admixture of fusel-oil or chloride of amyl, the quantity of carhqn obtained 
was lomewhat too large, and the phoiphorua somewhat too small. 

DecompoiUwns* 1. Phosphite of amyl passed in the state of vapour 
through a red-hot tube, yields gases among which phosphuretted hydrogen 
occurs. — 2. It may be set on fire by a flaming body when strongly 
heated; paper soaked in it burns, when set on fire, with a white phos- 
phorus flame. — 3. It absorbs chlorine gas, with rise of temperature and 
evolution of hydrochloric acid; in the dark at 0°, there is formed hereby 
a product containing 1 At. chlorine; but under the iufluence of heat and 
light, products very rich in chlorine are formed; these bodies are 
colourless and viscid, and decompose after a while, with evolution of 
hydrochloric acid. <-^ 4. Nitric acid acts violently on phosphite of amyl, 
yellow oily drops passing over, and a strong odour of valerianic acid 
being evolved.-— 5. When phosphite of amyl is boiled with solution of 
nitrate of silver, there is formed, with a certain amount of reduction, a 
black magma containing phosphate of silver. — 6. Exposed to moist air 
or kept in loosely closed vessels, it gradually turns acid. — 7* ^J boiling 
aqueous alkalis, it is quickly resolved into fusel-oil which passes over^ 
and a residue of alkaline phosphite. (Wurtz.) 



Amylophospliorous Acid. 

CioH»po« -s C^°H»»OSPHO*. 

Wurtz. N. Ann. Chim, Phy%, 16, 227; also Ann, Pharm. 5S, 7/i; abstr. 
Compt rend. 21, 358. 

Amylphosphorige Sdure, Acide amylophosphoreux. 

Formation (p. 15. — Preparation, After the oily mixture of phos- 
phite of amyl and amylophosphorous acid has been freed from hydrochloric 
acid by washing with water (p. 47), the amylophosphorous acid is 
extracted from it by means of dilute carbonate of soda (a strong solution 
of that salt would likewise dissolve the phosphite of amyl); the alkaline 
solution separated mechanically from the phosphite of amyl which floatd 
on the surface; the portion which still remains dissolved therein, sepa- 
rated by agitation with vinic ether; and the alkaline solution super- 
saturated with hydrochloric acid, whereby the amylophosphorous acid is 



AMVLOPHOSPHORIC ACID. 49 

separated, with strong turbidity, and at first rises to the surface in the 
form of an oil, in consequence of containing yinio ether, but sinks to the 
bottom after the ether is evaporated. Lastly, to free this oil from 
ehloride of sodium, it is dissolved in water, re precipitated by hydro- 
ehloric aeid, gently heated, after the aqueous hydrochloric acid has been 
decanted, and placed in a yacnum, to remove the water and hydrochloric 
acid. 

Pmperties. Oil which sinks in water, nearly inodorous in the fresh 
state, but strongly acid. 



IOC 


60-0 


.... o9*d7 .•• 
•... o'oA •■. 
.... 20-60 ... 
.... 31-50 ... 


Wurti. 
..... 39*47 


13 H 


13-0 


8-55 


P 

6 


31-4 

48-0 


19-72 

32-26 








Ciouispoe 


152-4 


.... 100-00 .. 


100-00 



DeoompasUionM, l.«The acid yields by dry distillation, a large quantity 
of combustible gas, and a small quantity of liquid distillate, leaving 
hydrated phosphorous acid, which, when more strongly heated, gives off 
puosphuretted hydrogen gas. — 2. Amylophosphorous acid burns with a 
very smoky flame and leaves the hydrate of phosphorous acid. — 3. It 
reduces silver-salts. — 4. After being kept for some time, it no longer 
dissolves completely in water, and the solution quickly decomposes into 
fusel-oil and phosphorous acid. The acid separated by hydrochloric acid 
from the soda-salt which has been kept for some time, likewise exhibits 
this behaviour. 

C<mbincUi(yM, Dissolves readily in waiei\ and is precipitated there 
from by hydrochloric acid. 

Decomposes the alkaline carbonates with effervescence. Its salts 
decompose readily. 

The potasf^ and soda-salts can only be obtained in the gelatinous 
state. 

The haryta-salt dries up in vacuo to a soft deliquescent mass. 

The lead-salt is a white curdy precipitate, which decomposes even in 
the dry state, and quickly when moist, giving off an odour of fusel-oil. 
(Wurtz.) 



f . Amylophosphoric Acid. 

CioH»PO* = C»H»0»,PHO*. 

Faedehick Guthrie. Chem, Soc, Qu. J, 9, 134; Ann. Pliarm, 09, 57. 

Fijrmaiion and Preparaiion, When equal weights of amylic alcohol 
and syrupy phosphoric acid are shaken up together in a flask, till perfect 
mixture takes place, they unite, producing considerable rise of tempe- 
rature, and the mass assumes a pale red colour. On leaving the mixture 
to stand for 24 hours at 60° to 80°, the colour changes to a deep wine red 
and amylophosphoric acid is formed. The acid liquid is then shaken up 
with warm water, which dissolves the amylophosphoric and a certain 
quantity of free phosphoric acid, leaving the uncombined fusel-oil undis- 
solved; the several aqueous solutions united, slightly supersaturated with 

VOL. XI. E 



BO AMTLENSt PRIMARY NUCLEUS .C»H» 

carbonate of potasli, and eyaporated nearly to drynees in the 
the residual maae, consisting of amylophosphate, phosphate, and carbonate 
of potash^ digested with warm alcohol to separate the two latter salts, 
and qaickly filtered; the solation, which contains all the amjlophosphate 
together with a smidl quantity of phosphate, again evaporated nearly to 
dxyness; the residue again exhausted with alcohol; and this operation 
several times repeated with continually stronger, and at last with 
absolute alcohol. The amylophosphate of potash may be regarded as 
pnre [free from phosphate L when a sample dissolved in water gives a 
snow-white precipitate witii nitrate of silver. The residue obtained by 
evaporating the alcoholic solution, is a yellowish transparent, gelatinous 
mass still containing amylic alcohol, to remove which impurity, the salt 
mast be dissolved in water, the solution evaporated to dryness over the 
water-bath, and this treatment repeated once or twice. A tenacious 
honey-coloured mass is thus obtained consisting of minute crystals of 
pure amylophosphate of potash. . 

To 00 tain the free acid, the dilute solution of the potash-salt is precipi- 
tated with sulphate of copper; the well-washed and Still moist precipitate 
suspended in water and decomposed by sulphuretted hydrogen; and the 
strongly acid liquid filtered as quickly as possible and evaporated to a 
syrup over the water-bath. At this stage of concentration, the acid 
suffers no further loss of weight when placed over sulphuric acid. When 
it is replaced on the water-bath, minute crystals are formed, which under 
the microscope appear to be long needles. 

FroperHes. Amylophosphoric acid is inodorous, has a strong acid 
taste and expels carbonic acid from its salts. It is much more stable 
than ethylophosphoric acid, inasmuch as it bears the heat of the water- 
bath without decomposition, the syrupy acid prepared as above, giving^ 
when dissolved in water and neutralized with ammonia, a perfectly white 
precipitate with nitrate of silver. Heated in the flame of a lamp, it 
Dums with a white flame, leaving a residue of phosphoric acid. 

Combinations, The acid is soluble in water. The crystallised acid 
absorbs moisture eagerly from the air, and deliquesces. 

The formula of the Amylophosphates is C»H"M«PO« = C^(Wm^)0\ 
PHO* = 2M0, C^«H"0,PO«.— The amylophosphates of the alkalies are 
soluble in water; the rest insoluble or sparingly soluble. They are, in 
general, more soluble than the corresponding terbasic phosphates. They 
all dissolve readily in nitric or hydrochloric acid. They are generally 
speaking, more stable than the corresponding ethylophosphates and ethy- 
losulphates, inasmuch as they bear the heat of boiling water without 
decomposition. 

When an electric current (from 4 Bunsen's cells) was passed througb 
a concentrated solution of amylophosphate of potash, separated into two 
portions by a clay partition, the electrodes being of platinum, hydrogen 
was liberated at the negative, and oxygen together with carbonic acid at 
the positive pole. The solution at the positive pole assumed an acid 
reaction, and smelt distinctly of valerianic or butyric acid (secondary 
products of decomposition). The liquid at the negative pole became 
alkaline, but remained odourless, showing that no amyl-componnd was 
there eliminated. From this experiment, and from similar results 
obtained with the amylosulphates and sulphovinates, Guthrie concludes 
that we are not at liberty to assume (as is commonly done) that the 



AMYLOraOSPHORIC ACID< 51 

organic oxides in ihene ftnd similftr salts are combined in the same 
manner- as the metallic Qxidee, but rather that the acid together with the 
organic oxide forms a congagated acid: 0. ^. in the amylophospbates s 
the phosphoric a<^d with the oxide of amyl forms a bibasic amyiophos- 
phoric acid. 

Amylopho$phaU of Ammonia. 2NH*0, C^°H"0, P0».— Obtained by 
decomposing the freshly precipitated copper salt suspended in water, 
with sulphide of ammonium, boiling the filtrate, filtering again, evapo- 
rating to dryness over the water-bath, and recrystallising from alcohol 
to remove sulphite and sulphate of ammonia formed during the reaction. 
AlsOj and in a state of greater purity, by neutralising amylophosphorio 
acid with ammonia. — Resembles the potash-Bait. 

Amylophaaphate of Fota$h, 2 KO,C*W*0,PO'. *— (Prq»«rfl«#ii p. 60). 
Tenacious, finely crystallised, translucent salt, without odour, but having 
the well-known taste peculiar to amyl-compounds. When exposed to the 
air, it absorbs moisture and deliquesces to a syrupy transparent liquid 
having a faint odour. Dried as completely as possible and then heated 
in a tube by itself, it yields fusel-oil. Heated on platinuita-foil in the 
flame of a lamp, it intumesces considerably, probably from escape of 
water, and then bums with a pure white flame, leaving a residue of pyro- 
phosphate of potash. Dissolves in all proportions in water either hot or 
cold; soluble also in alcohol, but insoluble in ether. 

Amylophotphate bf Baryta. — Precipitated from a solution of the 
potash-salt, on addition of chloride of barinm, in white scales having a 
silky lustre. From cold solutions, the precipitation is slow, but is accele- 
rated by heat, which more especially favours the formation of the scales. 
It collects chiefly on the surface of the liquid, probably in consequence 
of its &tty nature. 



2Ba 


... 137-2 
... 600 
... 110 
... 71-4 
... 240 


.... 4d*19 .1. 
.... 19-76 ... 
3-62 ... 
.... 23-52 ... 
.... 7-91 ... 


Guthrie. 
44-63 


10 C 


1900 


11 H! 


4-24 


P0». 

30 


23-45 

8-68 






2BaO,C»«H"O.PO« 


... 303-6 


.... 100-00 ... 


100-00 



Amyhphotphate of Lead,— Precipitated from a dilute solution of the 
potash-salt, on addition of acetate of lead. The precipitate, after 
washing and drying at 100°, is a bulky, white, anhydrous powder, without 
taste or smell. Dissolves readily in hydrochloric and acetic acids. 



2 Pb 


.... 2080 


.... 56-55 
.... 1603 
.... 294 
.... 1907 
.... 6-41 


Guthrie. 
66-4 


10 G 


„.. 60-0 


15-5 


11 H 


.... 110 


3-2 


PO* 

3 


.... 71-4 
... 24-0 


20-3 

4-6 








2PbO,CtoH"0,PO* .... 


.... 374-4 


.... 100-00 


100-0 



Amylophogphate of Copper, — Precipitated on adding a dilute solution 
of sulphate of copper, to a dilate solution of amylophoapfaate of potash. 

B 2 



52 AMYLENB: PRIMARY NUCLEUS C^BK 

The precipitate is at first almost white, bat gndoallj assumes a bluish 
tinge, and in the drj state is a light bine amorphoos powder. Bears a 
heat of 110*' without decomposing. 



2Cii.. 

IOC .. 

11 H .. 

PO» 

3 .. 



2CttO,C»H»0,PO» 230-4 







Guthrie. 


640 


.... 27-78 .. 


...... 28-1 


60*0 


.... 26-04 - 


...... 25-6 


11-0 


.•«• 4 / / •« 


4-8 


71-4 


.... 3099 .. 


30-4 


24 


.... 10-42 .. 


11-1 


30-4 


.... 10000 ., 


100-0 



In a lolution of fnercurtnu nitrate, amybphosphate of potash prodooes a precipitate 
in the form of a white amorphoua powder. 

AmylophogphaU of Silver, — Obtained as a white bulky precipitate on 
adding nitrate of silver to a solution of the potash-salt Turns grey 
when exposed to light, but remains white in the dark. Appreciably 
soluble in warm water, but does not separate in the crystalline form on 
cooling. Decomposed by long boiling with water, silver being deposited. 
Heated on platinum-foil, it turns yellow, and leaves pyrophosphate 
of silver. 



2 A? 

10 c .... 

11 H.... 
P0» 

3 O ... 







Guthrie. 


2060 


.... 56*48 


56-14 


600 


.... 15-69 .. 


15-28 


110 


.... £'oo i. 


3-29 


71-4 


.... 18*67 .. 


18-21 


24-0 


6-28 .. 


7-08 



2 AgO,CMH"0,PO» .... 382-4 .... 100*00 100-00 

When dry amylophosphate of silver is introduced into a tube, and 
moistened with a few drops of chloride of amyl, the tube then sealed 
and heated for several hours to about IKO^, decomposition ensues, chloride 
of silver being formed, together with an ethereal liquid, which may be 
dissolved out by alcohol, and precipitated therefrom in oily drops by 
addition of water. This oily liquid has an odour quite distinct from that 
of fusel-oil, and is probably the amylophosphate of oxide of amyl 
[terbasio phosphate of amyl], its formation being represented by um 
equation : 

2AgO,C»H"0,PO» + 2CWH»C1 - 3C»H"0,P0* + 2Aga. 

Amylophosphoric acid dissolves in aleohol, but is insoluble in ether, 
so that it is precipitated by ether from its concentrated alcoholic solution. 
(Guthrie) IT. 

Amylosulphorous Acid. 

C"H«S*0« = C»H"0*,2S0«. 

Erdmank & Gebathewohl (1845). J. pr. Chem, 34, 447. 
Medlock. Ann. Fhai^m, 69, 224. 

AmyUehw^ige 8'dure, Su^amyhehtorfeU&ure (Erdmann & Gerathewohl), Hypo- 
Mulphamylic acid, AmyluntenchwtfeUUure (Medlock), Aeide tuyoamylolique. 

Formation, The chief product of the action of nitric acid on amyl- 
mercaptan (Erdmann & Gerathewohl), or on sulphocyanide of amyl 
(Medlock), or on bisulphide of amyl. (Henry.) 



AMTL0SULPHUR0U8 ACID. 6Z 

Preparatiofu 1. Nitric acid of sp. gr. 1*25 is gently heated in a 
tabulated retort, and amjlmercaptan added to it, rerj gradually and in 
small portions, so that the mixture may not become too strongly heated, 
and no amylmercaptan may pass over nndecomposed with the nitrons 
vapours, — the action being continued so long as any signs of oxidation 
appear on heating. The acid layer at the bottom of the retort, consisting 
of amylosulphurous, nitric, and a small quantity of sulphuric acid, is 
then separated from the supernatant oily liquid, and evaporated over the 
water-bath till the odour of nitrous and nitric acid Is no longer }>ercep- 
tible; the remaining transparent and colourless syrup, — which consists of 
amylosulphurous acid contaminated with a little sulphuric acid, and may 
be used for the preparation of most of the amylosulphites (since these 
salts are soluble in alcohol, whereas the sulphites are insoluble; — diluted 
with water; the solution saturated with carbonate of lead, and filtered 
from the sulphate; and the filtrate treated with sulphuretted hjdrogen, 
again filtered, and evaporated to a syrup over the water-bath. (Erdmann 
& Gerathewohl.) — 2. A mixture of equal parts of sulphocyanide of 
amyl and moderately strong nitric acid is gently heated in a retort, after 
the first yiolent action has subsided, with cohobation, and occasional 
addition of nitric acid, till the last traces of the sulphocyanide have 
disappeared; the liquid which remains in the retort evaporated in a basin 
over the water-bath; the remaining red liquid dissolved in water and 
again evaporated to expel the last traces of nitric acid; the residual 
nearly colourless liquid, which contains a little sulphuric acid, diluted 
with water and saturated with carbonate of lead, the filtrate evaponted 
till it crystallizes; the crystals dissolved in water; the lead precipitated 
by sulphuretted hydrogen; and the filtrate evaporated over the water- 
bath. (Medlock.) 

Praperttea^ Transparent, colourless syrup, having a peculiar odour and 
ver^ sour taste, and not yielding crystals even in vacuo over oil of 
vitriol. ^Erdmann & Gerathewohl). Gradually solidifies in vacuo over 
oil of vitnol to a crystalline mass. (Medlock.) 

Decampariiian. The acid chars when heated, emitting a very repul< 
sive odour* (Medlock.) 

Combinations. The acid absorbs water from the air (Erdmann & 
Gerathewohl), and deliquesces. (Medlock.) 

The AmylosvlphiUs (or SvlfoamyloUtUs) are obtained, either by satu- 
rating the aqueous acid with the base or its carbonate, or by precipitating 
the baryta-salt with the sulphate of the corresponding base. They 
crystallise readily, and in external appearance resemble the etholysul- 
phites. (Erdmann & Gerathewohl.) Their formula is C^^H"M0',2S0'. 

The AmfMmiorKiU and the FotashsaUy crystallise in lamine, and 
dissolve readily in water and alcohol. (Erdmann & Gerathewohl.) 

Amyloiulphite of Baryta, — The filtered solution of carbonate of 
baryta in the acid is evaporated over the water-bath (or better, sponta- 
neously, according to Medlock). — Transparent, colourless laminsd, unctuous 
to the touch (having a pearly lustre, according to Medlock). They give 
off water at 100^, do not decompose at 160°, and bum with a bluish 
sttlplinr-flame at a stronger heat. (Erdmann & Gerathewohl.) Thev 
im anhydrous, and therefore safi*er only a trifling loss at 100 • 



54 AMYLSNBl PRIMARY NUCLEUS CM'HW 

(Medlook.)' Tbey move abont on water like biitjrate of 
dissolve in 10 pts. of water at 10°, in a smaller quantity of hot water, 
and likewise in alcohol. (Erdmann & Gerathewohl.) They dissolye 
rery readily in water and alcohol. (Medlock.) 



10 c 


60*0 
110 
68*6 
32-0 
48-0 


.... 27-32 . 
.... 501 . 
.... 31*24 . 
.... 14-57 . 
.... 21-86 . 


Erdmann U 

GorathewobU Medlock, 
26-92 .... 27-46 


n H 


5-03 .... 5*22 


% 8 


....... 31*31 .... 31*11 

15*33 


6 O 


21*41 






CWH»BaO».2SO» .... 


819*6 


.... 10000 . 


100-00 



AntylomlphUe of Lime, — Colourless lamins, easily solnble in water 
and alcohol. (Erdmann 4k Gerathewohl.) 

AmyUmdphite of Lead. — The salt purified by recrystallisation from 
alcohol^ forms colourless laminsa united in radiated groups, which give off 
2d'48 p. 0. [8 At] water at 120"^, turn brown at a stronger heat, giving 
off vapours having an exceedingly offensive odour and finally burn away 
with bluish sulphur-flame. (Erdmann <& Gerathewohl.) The aqueous 
solution yields by spontaneous evaporation, anhydrous silky needles, 
which w^en heated give off an extremely offensive odour and leave 
sulphide of lead. (Medlock.) The salt dissolves very readily in water 
(Medlock), and so stbundantly in hot alcohol, that the solution solidifies 
completely on cooling. (Erdmann & Gerathewohl.) 

Erdmann & 

Gerathewohl, Medlock, 
6i 100° til twetfo. mr-dried cfyttak. 

IQC 60 .... 23-53 24-02 2365 

11 H 11 .... 4-32 4-64 4-23 

Pb 104 .... 40-78 40-58 40*67 

2S 32 .... 12-55 

6 48 .... 18-82 

CM>H»PbS20« 255 .... 10000 

Ouprie JmylomdpkUe. — Blue green tables wbioh, when placed ever 
oil of vitriol, even at ordinary temperatures, give off water and become 
opaque. (Erdmann & Gerathewohl.) When the acid saturated with 
carbonate of copper, is evaporated to dryness over the water-bath, the 
residue extracted with alcohol^ and the filtrate left to evaporate spon- 
taneously in a narrow vessel, anhydrous crystalline lamina are obtained. 
(Medlock.) 



10 c 


60 


.... 32-80 . 
6-01 ., 
.... 17*48 . 
.... 17-48 
.... 26-23 


Medlock. 
32-64 


11 H 


11 


6-16 


Cn 


32 


17-83 


2 S 


32 




6 


48 










CWH"CuS«0»..., 


183 


.... 10000 





' AmylosulphUe of Silver, — - The acid saturated with carbonate of bilvcr, 
yields, if not too much evaporated, transparent, colourless, rhombio tables; 



AMYLOStJLPHURIC ACID. 55 

buV if too maoh ooncentnted, it solidifies to an amorphous jelly, like 
'Coagulated white of egg, and appearing under the microscope to consist 
of fine interlaced hairs. (Erdmann & Gerathewohl.) 



10 c 


At 100 


« 

60 

11 

108 

32 

48 


.... 23- 16 . 
.... 4-25 . 
.... 41-70 . 
.... 12-36 
.... 18-53 


Erdmann St 
Genthewohl. 
21-28 


11 H 




3-99 


A« 

2 S 

6 O 




43-89 









CiOH»AgS20« 259 ..., 100*00 

Danson {Ckem. Soe. Qn. /• 3, 158) prepftreaamylotnlphiiroiis acid from bisulphide 
of amyl and nitrio acid. 



Amylosulphnric Acid. 

4 

CAROiTBa (1839). Ann. Ckim. Phys, 70^ 86; also J. pr, Chem. 17, 216. 
Kekul^. Ann. FhaiKn. 75, 275. 

StUpKamylic acid, Amy^chwrfeUSure, 

Preparation. A mixture of equal parts of fusel-oil and oil of vitriol 
(after standing for some time^ till water no longer separates f nsel-otl from 
it; KekuU) is diluted with water; the resulting cmde amylosvlphuric acid 
saturated with carhonate of > baryta ; the solution filtered from the 
sulphate of baryta and evaporated; and the crystals of amylosnlphate of 
l>aryta which separate after cooling, are freed from the mother-liquor upon 
blotting paper, and purified by shaking up their aqueous solution with 
animal charcoal, and twice crystallising by spontaneous eyaporation. The 
jpolution of these crystals, precipitated by the proper quantity of sulphuric 
|u;id, then filtered and eyaporated, yields the pure acid. (Gahour8.)^-Kekni6 
prefers preparing the lead-salt and decomposing it with sulpheretted 
nydrogen, after which he carefully evaporates the colourless filtrate to a 
thin syrup. 

Properties. Colourless, thin syrup which sometimes deposits slender 
needles by spontaneous evaporation. (Kekul6 did not obtain any 
crystals.) Tastes acid and bitter (sharply acid, according to Kekul^), and 
reddens litmus strongly. (Cahours.) 

Decompositions. 1 . The concentrated aqueous acid decomposes spon- 
taneously into fusel-oil and sulphuric acid, slowly in the cold and in 
vacuo (or when exposed to the air; Kehdi), quickly on boiling (Cahours), 
the more quickly as it is more concentrated. (Kekul6.) — 2. It is decom- 
posed by chlorine in the cold, and by nitric acid when heated. (Kekule.) 

Cimbination^. The acid dissolves very readily in water. (Cahours.) 
The Amylosulphates or SulphamykUes are for the most part = 



56 AMYLUNE: PRIMARY NUCLEUS C>*Hw. 

C»°H"M0',2S0l (Cahouw). They are generally crystallisable, hara 
a bitter taste, and are eoapy to the touoh. The crystals generally 
contain vrater and in that case are often efflorescent. (Kekal6.) When 
their aqueous solution is boiled, they are resolved into sulphate, free 
sulphuric acid and fusel-oil. (Cahours.) This decomposition takes place 
slowly at ordinary temperatures, even in the crystallised salts; never- 
theless, these crystallised dalts may generally be dehydrated at 100^ 
before decomposition begins. (Keknl6.) For the decomposition by diy 
distillation see the Itme-salt. All amylosulphates dissolve in water (Cahours]^ 
and in alcohol, very sparingly in ether. (Kekul^.) 

Amylosulphate of Ammonia, •— The filtrate obtained by precipitating 
the lime-salt with carbonate of ammonia, yields by spontaneous evapora- 
tion, colourless, bitter crystalline scales, and by evaporation over the 
water-bath, a nodular crystalline mass. The crystals give off nothing at 
100°, begin to decompose at 140°, and burn away leaving a residue of 
charcoal. They deliquesce slightly in damp air, and dissolve very 
readily in water, on which they move briskly about; they are lees 
soluble in alcohol, and insoluble in ether. (Kektu6.) 

CrygtahT Kekold. 

10 C CO .... 32-43 .M 32-36 

N 14 .... 7-57 

15 H .'. 15 .... 8-11 8-33 

2 O 16 ... 8-65 

2 SO» 80 .... 43-24 

CM'H"(NH<)0»,2S0» .... 185 .... 100-00 

Amylomlphate of Potash. — The solution yields by spontaneona 
evaporation^ colourless tufts of needles, having a very bitter taste 
^Cahours), or, nodules composed of needles having a silky lustre. 
(Kekul6.) These crystals effloresce on exposure to the air, and turn 
slightly brown, giving off fusel-oil and sulphuric acid. In vacuo or at 
100°, thejr give off 399 per cent (1 At) of water, without further 
decomposition, swell up strongly at 170°, then melt, and leave a black 
scum. ^Kekul6.) The salt dissolves readily in water and in weak 
alcohol (OahoursV less readily in strong alcohol, from the hot solution In 
which it crystallises in slender needles, and is insoluble in ether. 
(KekuU.) 

Dried in vacuo. Cahoan. Kekul^. 

IOC 60-4 .... 2910 .... 29-39 

11 H 110 .... 5-33 .... 5-13 

8-0 .... 3-88 .... 3-89 

KO,SO« 87-2 .... 42-29 .... 42-21 .... 42-39 

S0» 400 .... 19-40 .... 19-38 

CWH»KO»,2SO» .... 206-6 .... 10000 .... 100-00 

AmplosulphaU of Soda. — By precipitating the lime-salt with car- 
bonate of soda and spontaneous evaporation of the bitter filtrate, nodules are 
obtained set with small crystals. These swell up at 35° [1351] softening, 
and giving off water, and begin to undergo further decomposition at 145 . 
They dissolve abundantly in cold water and in all proportions in hot 
water; from hot alcohol they crystallise in long radiated lanlinie; they 
do act dissolve in ether. (K.ekuU.) 



AMTLOSULPHimiC ACID. 57 

OryUaU dried between paper. Kek«U* 

CMH"0 790 .... 36-38 

NaO,SO> ^ 71-2 .... 32-78^ 32-82 

S0> 40-0 .... 18-42 

3 HO 27-0 .... 12-42 12-19 

CMH"NaO»,2SO» + 3Aq.... 217-2 .... lOO'OO 

Atnylosidphate of Baryta. — Preparaium (p. 55).— On tlie wuhee of the 
add nentralued with carbonate of baryta and filtered, there generally floata a brown oil, 
which, after eraporation, may be aeparated by eraporation through a wet filter; any 
accidental oolonring of the filtrate if easily r e mored by agitation with charcoal. (Keknl^.) 
— LamintB having a strong pearly lostre and very bitter taste ^Cahonrs)! 
or, bj spontaoeoas eyaporationi large, very flexible^ rhombic tables. 
(Kekule.) The crystals effloresce in dry air and giyes off 6-66 p. c. (the 
1 At.) water in vacuo. They begin to decompose at 95°, molting at the 
same time, if they have not been previously dried. (Keku)6.) They 
give off an oil somewhat above 200^ and leave sulphate of baryta mixed 
with charcoal. Their aqueous solution is resolved by longer boiling, into 
fusel-oil, sulphuric acid, and sulphate of baryta. They dissolve very 
readily in water, more readily in warm than in cold alcohol, but are 
insoluble in ether. (Cahours.) 

Cahonra, Medlock, 
Cryetaie dehydrated at 100*. at 100*". cold in vacuo* 

IOC 60-0 .... 24-58 .... 24*36 

12 H 12-0 .... 4-91 .... 4-93 

2 16 .... 6-54 .... 6-86 

BaOS0» 116-6 .... 47-67 .... 47*45 .... 47*43 

«0» 40-0 .... 16-35 .... 16-40 

C»H»BaO»,280» + Aq 244-6 .... 100-00 .... 100-00 

Air^dried cryetaie. Keknl^. 

IOC 60-0 .... 23-66 

13 H 13-0 .... 5.13 

3 24-0 .... 9-45 

BaO.SO" 116-6 .... 45-98 .... 4593 

SO» 40-0 .... 15-78 

C»H"BaO«,2SO» + 2Aq .... 2536 .... 100-00 

AmyloBulphaie of Slroniia. — White crystallised nodules, which turn 
brown in the air; leave 39' 8*2 p. c. sulphate of strontia when ignited, and 
therefore contain 2 At. water; dissolve readily in water and weak alcohol, 
with difficulty in absolute alcohol, and not at all in ether. (Kekul6.) 

AmyIo9tdphate of Lime. — The crude acid is saturated, first, to avoid 
unnecessary effervescence, with hydrate of lime, which however must not 
be added m excess, and afterwards with chalk; the evaporated filtrate 
mixed with alcohol to precipitate the whole of the gypsum; and again 
filtered and evaporated. (Kekul6.) — White crystalliue nodules, greasy to 
the touch and having a bitter and slightly pungent taste. (Cahours!) — The 
crystals effloresce in dry air and give on 8*55 p. c. (2 At.) water in vacuo. 
When kept for some time or heated in the water-bath, they slowly give off 
fnseUoil. When gradually heated from 100° to 150^ they turn soft and 
blacken, and give off first, sulphurous acid, a small quantity of carbonio 
aoid, and a combastible vapour, and lastly more carbonic aoid* together 



SS AMYLBMB : PUHAHT VUCLBUS C^H^. 

with suldhur, Vhile salphacto of lime and oharooal Tenmin behind. The 
combustible Ti^poor oopdensee to an oily mixture (oontamihated with a 
sulphur-compound) 6f amyleiie C^®H^^, and amjlic ether G^^H^K), which 
increases in the course of the distillation. — By repeated fractional distil- 
lation of- this oily mixture, the more rolatile amylene is obtained in the 
form of a colourless oil; which floats on water, boils steadily at 42°, has a 
vapour-density of 2*4271, is tasteless, but has a slight smell of onions 
arising' from the admixed snlphnr-coropoulid. It contains 83 '50 p. c. C 
and 14*55 H. — The amylio ether, which is likewise contaminated with a 
sulphur-compound, does not exhibit any constant boiling point, and is 
partially decomposed at each recti fication^ the residue turning brown. 
The portion which distils over between 165° and 175°, contains 73*96 
p. 0. G ld'54 H and 12*50 0. Cold nitric acid forms with it a purple 
mixture without decomposition: and oil of vitriol forms a red syrup, from 
both of which, water again separates the colourless oil. (Kekul6.) — 
IT. Amylosulpbate of lime mixed with alcoholic ammonia and heated to 
250° for two hours in a sealed tube, yields a mass which when distilled 
with potash gives off aniylamine. 

CiOH"CaO»,2SO» + NH» = CWNH» SHO + CaSO<. 

solpbate of 
amylamiDe. 

SulphoTinate of baryta heated in a similar maimer with ammonia appears to give off 
etbylamine. (Berthelot, Compi. rend, 36. 1098. %) — Amylosulphate of lime 
dissolves readily in cold, less readily in hot water, whence a solution 
saturated' in the cold, becomes turbid on boiling. (Gahours.) [From the 
presence of gypsum 1]. The hot aqueous solution solidifies on cooling ; 
it effloresces strongly when evaporated. The salt does not dissolve in 
hot alcohol more readily than in cold; it does not dissolve in ether. 
(Kekule.) 

Air^dried erystaii. Cahonrs. 

10 C 60 .... 30-62 3100 

12 H 12 .... 6-12 6-00 

2 O 16 .... 8-16 8-12 

CaO,50' : 68 .... 34*69 34*63 

SO" 40 ,... • 20-41 20-25 ' 



C*®H**CaO,2SO» + Aq.,.. 196 ...100*00 ........ 100-00 

According to KeVul^j the recently prepared crystals contain 2 At. water (vid^ nfp.) 

Amylo9ulphate of Magneda, — The solution of carbonate of magnesia 
in the pure aqueous acid, yields by spontaneous evaporation^ transparent, 
colourless^ nacreous, elongated, rhombic lamin», which are with difficulty 
deprived of the whole of their 4 At water, leave 28*2 p. c. sulphate of 
magnesia when iffuited in the air, and dissolve in water and alcohol, but 
not in ether. (KekuU.) 

Amylotulphate of Alumincu'^-'The colourless acid solution of hydrate 
of alumina in the acid, leaves, when evaporated in vacuo over oil of 
vitHol, a bitter jelly, which soon decomposes on standing, quickly deli- 
Gfnesoes in a damp atmosphere^ dissolves also in alcohol and ether. 
(Kekul^) ... 



AMTLOSULPHUBIC ACID. f(9 

t Amylomtpkoie of Manganese-^The pale red soldtion of oarbonaie of 
maDganese in the pare acid, yields in yacuo^ n^rly colouriessi trans- 
parent needles, permanent in the air. These crystals ignited in contact 
with acr, lealve d2*92 p. e. 'sulphate of manganese, and uierefore contain 
4 At water. Their aqneons solution exposed to the air, slowly deposits 
brown nodules which precipitate chloride of barium. The needles 
dissolre also in alcohol but are insoluble in ether. (Kekul^.) 

a 
»^ 

Amfflostdphate of Ziiic, The solution of carbonate of sine in the acid 
depoedts on evaporation nacreous lamins, which decompose at 1 1 0°^ and 
dlssolye in water and in alcohol. (Kekule.) 

CryniaU dried between paper. Kelral^. 

Ci"H"0,2S0» 159-0 .... 7S*20 

ZnO 40*2 .... 18*51 18-50 

2 HO 180 .... 8-29 8-49 

C«>H"ZnO«,2SO" + aA.q .... 217-2 .... 10000 

• 

AmylogulphaU of Lead. — a Bihasic The aqueous acid or the lead 
salt b is saturated by digestion with oxide of lead. The colourless neutral 
filtrate deposits small crystals; when quickly evaporated, it leaves a 
colourless viscid mass ; when exposed to the air, it becomes covered with' 
a film of carbonate of lead, and passes into the salt b. (Kekul6.) 

b. Monobasic, — Obtained by dissolving carbonate of lead in the acid. 
(Cahonrs.) By carefully evaporating the filtered solution of white lead 
in the crude acid, ultimately over oil of vitriol at ordinary temperatures. 
rKekul6.) — White laminoQ having a sweet and somewhat bitter taste 
(Cahours); colourless^ bitter-sweet, crystalline nodules, which redden 
litmus. (Kekul§.) The crystals dried between paper, leave, when ignited 
in the air, 52-82 p. c. (54*91, according to Kekul^) of sulphate of lead; 
they are therefore = C**H"PbO»,2SO« H- Aq. (Cahours.) The aqueous 
solution deposits sulphate of lead, slowly when kept, quickly on boiling. 
(Cahours.) The salt dissolves* very readily in water (Cahours), readily in 
alcohol, but is insoluble in ether. (Kekule.) 

Ferrous AmylosiUphate.-^The aqueous acid in contact with iron,^ive8 
off hydrogen, and forms a pale green, sweetish bitter solution which reddens 
litmufi/j and when evaporated, deposits brown flakes of ferric oxide^ and 
deposits pale green crystalline grains. These crystals quickly tarn yellow 
on exposure to the air, dissolve in water and, alcohol, and with green 
colour in ether. (Kekule.) 

Ferric Amylosulphate, — The yellow solution of ferric hydrate in the 
afiid, yields, on evaporation, small yellow^ easily decomposiUei deliques* 
cen^ crystalline granules. (Kekule.) 

AmyUmdphaU of CobalL — By piecipitating the baryta-salt with suU 
phate of cobalt, and evaporating the filtratOi rose-colooied laminae are 
obtained very soluble in water. (Cahours.) 

AmylosulphaU of Nickel,'-^ The solution of the hydrated oxide in the 
acid, yields by evaporation, green elongated laminie united in nodules, 
which deliquesce in moist air, dissolve in water and alcohol, but are 



60 AMYLENB: PRIMART NVCUUS C»U» 

Inaolnble in ether. Thej contun IT'S p. e. oxide of nickel, and therefore 
2 At water. (Keknl4). 

Ouprie AmyUmUphate.'^ Greenish bine, silkj, verr thin lamino, yeiy 
floluble in water. (Cahonrs.) The bine solution of oaroonate of oopper in 
the aoid yields, when left orer oil of vitriol, laige elongated tables whioh 
are permanent in the air, contain 17*05 p. c. cnprio oxide, therefore 4 At 
water, dissolve readily in water and weak alcohol, less readily in absolute 
alcohol, and are insoluble in ether. (Kekul6.) 

Mercuric Amylomlphate,'-^ The yellow solution of mercuric oxide in 
the acid yields by evaporation in vacuo, dark yellow, crystalline nodules 
soapy and glutinous to the touch, having an extremely sharp and bitter 
taste; they contain 37*8 p. c mercuric oxide, and therefore 2 At water; 
they decompose after keeping for some time and deliquesce in damp air. 
(Kekul6.) 

Amylondphaie qf SUver.^^ The solution of carbonate of silver in the 
slightly heated acid yields by evaporation, colourless laminie which 
dissolve very easily in water. (Cahonrs.) Colourles scales grouped in 
nodules, which blacken on exposure to the air, and dissolve in alcohol 
but not in ether. (Kekul6.) 

Cnf$iat$ drUd in voctio. Keknl^. 

C«»H"0*.2S0» 167 .... 60-73 

Ap 108 .... 39-27 39-33 

CWH»AgO»,2SO» 275 .... 100*00 

Amylosulphuric acid dissolves readily in aUohcl* (Cahonrs.) 



AmylozantMc Acid. 

C»*H'«S*0» = C"H»0»,2CS»* 

Erdmann. (1844). J. per Ckem, 31, 4. 

Balabd. iv, Ann. Chim, Phys. 12, 294; also <7. pr. Chem, 34, 135* 

Xanihamylie aeid, Sulphocarb<mat€ ^f amyh 

Preparation. A cold-saturated solution of hydrate of potash in fusel- 
oil is mixed with bisulphide of carbon, till the alkaline reaction disap- 
pears, a certain amount of heat being thereby evolved; the crystalline 
pulp which forms on cooling thrown on a filter; the pale yellow, shining 
crystalline scales washed with ether, and freed from the yellow mother* 
liquor by repeated pressure between paper; and the amyloxanthic acid 
separated from them by hydrochloric acid in the form of an oil, which 
most be dried over chloride of calcium, to jpreserve it from decomposition. 
(Erdmann.)— -2. A solution of hydrate of potash in fnsel-oil is mixed 
with a solution of sulphide of carbon in fusel-oil; and the scales which 
form on cooling separated from the yellow mother-liquor, pressed between 
paper, and purified by crystallization from hot alcohol or ether. (Balaid; 
eomp. Koninck, Bert. Jahre/iier^ 24, fih%^ 



AMTLOXAMTHIC ACID. 61 

ProperiUi. Colonrleai or pale yellow oil, which is somewhat heavier 
than water, has a disagreeably penetratiDff odour, colours the skin deep 
jcllow^ and reddens litmus, (firdmann.) Yellow oil. (Balard.) 

12 C ..„ 72 43-90 

12 H 12 7-32 

2 16 9-76 

4 S 64 39-02 

C'«H»*0»S< 164 10000 

The add bums with a laminons flame and decomposes when kept in 
the moist state. (Erdmann.) 

T. Jmylaafanihate ofJsnmonia C^^H^^(NH*)0*,2CS*.— Produced, toge- 
ther with xanthamylamide, by the action of ammonia on bioxysulphocar- 
bonate of amy], (vid. inf,): 

2C«H"0*S< + 2NH* - C»NH"SK)* + Cm>H"(NH^0«,2CS« + 2S. 

Thb salt is contained in the liquid filtered from the xanthamylamido 
and sulphur, and crystallises from an alcoholic or ethereal solution in long 
colourless prisms. From a cold aqueous solution evaporated in vacuo, it 
also separates in prismatic crystals, but is gradually decomposed by 
water, with formation of an oily liquid. Even the dry crystals decom- 
pose on exposure to the air, yielding sulphocyanide of ammonium, and 
a yellow oil not identical with xanthamylamido. When the aqueous 
solution of the salt is evaporated over the water-bath, it volatilises toge- 
ther with the watery vapours. It may be sublimed by a very gentle heat; 
but when more quickly heated in a current of dry air, it decomposes, and 
at last suddenly, with effervescence, evolution of sulphide of ammonium, 
and formation of a turbid yellow liquid, from which water dissolves 
snlphocyanide of ammonium, and separates amylic alcohol; canstic potash 
decomposes the salt, with evolution of ammonia, even in the cold, and 
qnickly when heated. — Hydrochloric acid added to the aqueous solution, 
separates a volatile oily acid, having a suffocating odour and insoluble in 
water. (M. W. Johnson, Chem, Soc Qu, J. 5, 147.) IT. 

AmyloxanUiaU of Potash crystallises in pale yellow, shininfl, crystalline 
scales, greasy to the touch. (Erdmann, Balard.) They dissolve in water, 
forming a yellow very bitter liquid. (Balard.) Thev dissolve abundantly 
in hydrated and in absolute alcohol, sparingly in ether. (Erdmann.) 



12 C 


47-2 

72-0 


.... 23-34 .. 
.... 35-61 .. 
.... 5-44 .. 
.... 3-96 
.... 31-65 


Balard. 

22-9 

35-4 


11 H 


11-0 


6-3 


O 

4 S 


8-0 

64*0 











C»H"KO»,C»S< 202-2 .... 10000 



AmyhxanUiaU of Lead. — The aqueous solution of the potash salt 
forms with acetate of lead, a white precipitate which turns black when 
boiled. (Erdmann.) — IT. The aqueous solution of the ammonia-salt forms 
with acetate of lead, an adhesive, yellow, semi^solid salt, which gradually 



69 AMYLBNK: PRIMART NUCLEUS C»H». 

d6Gompo«60 and turns brown; bat on addinff tbe aqneonii^ flotation of the 
aynraonia or potash-salt mixed with alcohol, to an aleoholio solution of 
acetate of lead^ till a precipitate begins to appear^ and then adding, 
alcohol in excess, a clear solution is obtained^ which, by spontaneous 
evaporation deposits the lead-salt in delicate, shining^ plates containing 
38*32 p. c. lead, (calculated quantity == 38*85). By aeconiposing the 
recently precipitated lead- salt suspended in alcohol, with sulphuretted 
hydrogen, an acid liquid is obtained, which gives a yellowish white preci- 
pitate with alcoholic acetate of lead, and lotiaB a crystaHine salt with 
potash. (Johnson.) %. 

The aqueous solution of the potaeh-salt forms with cupric iulphaUy 
lemon-yellow flakes; with mm*curic chloride, a white precipitate which 
remains white when boiled; and with nitrate of tUffer, a white precipitate 
which quickly blackens on boiling or on exposure to light (Erdmann.) 
The ammonia-salt forms with nitrate of silver a yellow ourdy precipi^ite. 
(Johnson.) 

^ Meihttmylie and VitiomyUe (ktytulphoeorbanatei qiouu [2CS*0, and 

^M|,,i>2CSK>. — Obtained by distilling a mixture of amyloxanthate of potash and 
snlphomethylate or sniphonnate of potash \ e. g, 

^"^"}2CS«0 + ^^*}280* = ^o^ii}2CSK) + 2K0*. 

The methamylic compound heated with dry ammoniacal ga«, and digested with it for 
several monUis, yielded a substance having all the properties of zanthamylamide : 

^oyu } 2CS«0 + NH« - C»«NHttO»S* + (?H*S>. 



* .. > 



zanthamylamide. methyl 

mercaptan. 

[Compare the reaction obtained by Debns with vinomethylic ozysnlphocarboBflie, 
(viii, 445)]. The yinamylic ozysulpbocarbonate digested with ammonia yielded a 
yellow miztare which emitted tbe odour of amylic mercaptan, but did not appear to form 
zanthamylamide. (Johnson.) [If amyl-mercaptan were formed, the other product 
most have been zanthamide.] 



Bioxysulphocarbonate of Amyl. 

C"H"0'S* = C«H"0«,C^* = C^<>H"0,(?S*0. 

Desains. N, Ann. Chim. Phy%, 20, 496; also J. pr. Chem, 42, 299. 

When hydrate of potash and fusel-oil free from spirit of wine, are rubbed 
together in a mortar to a thin pulp; sulphide of carbon then added, but not 
in excess, while the trituration is continued; the resulting amyloxanthate 
of potash diluted with a small quantity of water; and pulverised iodine 
triturated at the bottom of the liquid, very slowly, to avoid too great a 
rise of temperature and consequent separation of sulphur, bioxysnlphocar- 
bonate of amyl rises to tbe surface of the watery liquid containing iodide 
of potassium, in the form of a yellow oil. (Desains.) — f Johnson {Oh^nu 
Soc, Qu, J. 5, 142) introdnees the amyloxanthate oi potash into a flask 



. ' KITRITE OP AMTL. 63 

together with a qcuuitity of enlphide of carbon sufficient to convert it into 
a very thin paste, then introduces iodrne> which is immediately decolorised, 
with evolution of heat. On agitation, a grey mixture is formed consisting 
of roundish granules of iodide of potassium, and a yellow mobile liquid. 
The whole thrown on a filter and washed with sulphide of carbon, yields 
a filtrate, which on distilling off the sulphide of carbon, leaves bioxy- 
Milphocarbonate of amyl in the form of a yellow oily liquid. ^. — 

Dried over chloride qf ealeiwn. Desains. 

12 C 72 .... 44*17 43-96 

11 H 11 .... 6-7& 7-13 

4S 64 ... 39-26 

2 O 16 .... 9-82 

C»H"»S*0« 163 .... 100-00 

When bioxysulphocarbonate of amyl obtained as above, is gradually 
heated in an oil-bath, it boils at 187°; and if the receiver be changed at 
this point, an amber-coloured, oil collects, having a strong ethereal odour 
and containing 55-0 p. a C and 9*4 H, therefore =C^'H^^OS'. (Desains.) 



Nitrite of Amyl. 
(^•H"NO^ = C"H"0,NO» 

Balabb (1844). If. Ann. Chim. Phys. 12, dl8 
RiECKHER. Jakrh. pr.,Pharm. 14, 1. 

Bdlpetrigaaures Amyloxyd, Salpetrigmyleater, Ether azoti^amyliquef Ether 
maotewf de VAleool ampUque. 

Preparation.. 1 . Fusel-oil is gently heated in a retort with nitric 
acid; the fire quickly removed as soon as bubbles begin to form; the 
retort cooled if the effervescence is too strong; the portion of the distil- 
late which passes over below 100° (that which goes over between 100° 
and 1 48° is contaminated with nitrate of amyl, according to HofmaunX 
rectified over potash, whereupon ammonia is evolved from the hydrocyanic 
acid previously formed; and the product which distils over at 96 col- 
lected apart. (Balard.) — 2. The nitrous vapours evolved from starch 
and nitric acid are passed into fusel oil. (Balard.) This liquid is distilled, 
the nitrous vapours being passed through it all the time; and the distillate 
ifl rectified, the portion which distils over at 95° being collected apart. 
(Rieckher.) 

Propertiei, Pale yellow liquid, which assumes a darker yellow colour 
whenever it is heated, boils at 06°, and yields a reddish yellow vapour of 
density 4*03* (Balard.) Sp. gr. 0-8773; boiliuff point 95°. (Rieckher.) 
Begins to boil at 90°, the boiling point rising slowly to 110°, while red 
vapours are evolved, then more quickly to 200°, and leaves a small 
quantity of charcoal. (W. Hofmann, Ann. Pharm. 75, 364.) Smells like 
nitrite of ethyl (Balard), and produces violent head-aehe when its vapour 
id inhaled. (Rieckher.) 



31 



AMYLBNB: PRIMABY NUCLEUS CH". 









Balard. 


Riedcher. 


Aw \y ••••••••■•••••! 


..••• ou •*.. 


51*28 .... 


50*3 . 


....... 51*23 


11 H 




9*40 .... 
11*97 .... 


9*5 . 
13*6 


975 


N 


14 .... 




4 


• t«»« O^w ••■• 


27*35 ... 


26*6 




C>«H»NO* 


• •««• kli •••• 


100*00 .... 


100-0 




C-Tapoar .... 

a1 <»ffftB. ..•...• A*** 




Vol. 

10 

11 




Denutjr. 
4-1600 
0*7623 


N-gu 

O-gM 




1 

2 




9706 




2*2186 


Vapour of Nitrite of Am jl 


2 

1 




81115 


■ • ■ ■ • ••■ ■•••■•• 


4-0557 



Decompontions. 1. Nitrite of amjl is decomposed b^ peroxide of 
lead with the aid of heat, yielding fusel-oil and nitrate and nitnte of lead ; 

2CMH"NO* + 2PbO» + 2HO « 2C»H»0» + PbO,NO» ♦ PbO,NO» (Ricckher). 

2. It is but slowly decomposed by aqueous potash (Balard), more quickly 
by alcoholic potash, with formation of nitrite of potash. (Rieckher.)-*> 
d. When dropped upon melted hydrate of potash, which sometimes seta 
it on fire, it forms valerate of potash. (Rieckher.) 



Nitrate of Amyl. 

C»H"NO« = C^'^H^CNO^. 

WiLH. HoFMANN (1848). iV. Ann. Chim. Phyi. 23, 374; also J. pr. 

Chem. 45, 358. 
RuBCKHBB. Jahrb.pr. Fharm, 14, 1. 

Fannation, When fusel-oil is distilled with nitric acid, nitrite of 
amyl first passes over, then from 90^ upwards, a mixture of nitrite and 
nitrate. (Hofmann.) 

Preparation, 10 grammes of nitrate are shaken up in a retort for 10 

minutes with 30 grammes of strong nitric acid, 40 grammes of fusel-oil 

then added, and the mixture gradually heated, a cooled receiver being 

adapted to the retort. With larger quantities, the action is so violent 

that scarcely anv nitrate of amyl is obtained. The distillate, which 

collects in two layers, is shaken up with water; the lower layer, after 

standing for some time, separated by a funnel, then rectified, the receiver 

being changed after the boilin|^ point has risen from 110^ to 148'' and 

become stationary; and the portion which distils over from 148^ upwards 

rectified twice more, the liquid which goes over below 148^ being each 

time set aside. (Hofmann.) Nitrate of ammonia may be used ioatead of nitrate 
of nrea. (Rieckher.) 

Properties. Colourless oil of sp. gr. 0*994 at 10^; boils at 148^ 
(Hofmann.) So. gr. 0*902; boils at 137^ (Rieckher.) Has a peculiar 



BIBASIC SILICATE OF AMYL. 65 

odour like that of bags, and has a sweet and burning taste, with very 
disagreeable aftertaste (Hofmann); its odour is more agreeable than that 
of any other amylic ether except the acetate. (Rieckher.) 

Hofmann. Rieckher. 

IOC 60 .... 4511 .... 45-65 4513 

11 H 11 .... 8-27 .... 8-70 8-48 

N 14 .... 10-53 .... 11-25 

6 48 .... 36-09 .... 34*40 

C»H"NO» 133 .... 100-00 .... 10000 

Nitrate of amyl bums with a faint green-edged flame. — Alcoholic 
potash decomposes it into fusel-oil and nitrate of potash. (Hofmann.) 

It dissolves in ether and alcohol, and is precipitated from the latter by 
water. (Hofmann.) 



Bibasic Silicate of Amyl. 

C*>H»SiO* = 2C«»H"0,SiO«. 

Ebblmen. (1846.) y. Ann. Chim. Phyi. 16, 155; also Ann. Pharm, 57 
344; also J. pr. Chem. 27, 367. 

Ktetelitmrei Amylosyd, HalbkieaelmyUtter, Silicate amylique. 

Formation. Chloride of silicium takes up the first quantities of fusel- 
oil, with depression of temperature and rapid evolution of hydrochloric 
acid; the following portions, with rise of temperature and slight evolution 
of hydrochloric acid: 

2Ci0H»O> + SiCP - C»H«SiO< + 2HC1. 

Preparation. On distilling a mixture of the two liquids, hydrochloric 
acid and the excess of fusel-oil pass over first, then from 320 to 340"^ (a 
slight residue then remaining) the silicate of amy], which may be 
parified by two rectifications, the first and last portions being each time 
set aside. 

Propertiei, Transparent colourless liquid of sp. gr. 0*868 at 20°, 
boils at 322"" to 325". Vapour-density 11*70 ^the residue in the bulb 
however appears browned). Has a faint odour like that of fusel-oil. 

£belmeii. 

20 C 120 .... 63*50 .... 63*78 

22 H 22 .... 11*64 .... 11-69 

2 16 .... 8-46 .... 8-52 

SiO» 31 .... 16-40 .... 16-01 

C"H«SiO* 189 .... 100*00 .... 100,00 

Vol. Density. 

C-yapour ...t 20 8-3200 

H-gas 22 1-6632 

Si-voponr? 1 1*0400 

O-gaa 2 2-2186 

Vapour of C»H«SiO*.... 1 132418 

* OL. XI. P 



C6 AMYLENE: PUIMARY XLCI.EUS C»oHW 

It mutt be obsenred that, according to ibis oalculatton, tbe vaponr of bibasic 
Bilicate of amyl, like tbat of the corresponding ethyl compound (Tiii, 479), is not 
diatomic but monatomic. 

Decompositions, 1 . Bibasic silicate of amyl bums with a long white 
flame, and deposits silica in the form of a very soft powder. — 2. It is 
very slowly decomposed by water, in which it does not dissolve. — 3. It 
is decomposed by alcoholic soda but not by alcoholic ammonia. 

Combinations, Silicate of amyl mixes in all proportions with alcohol, 
ether, and fusel-oil. (Ebelmen.) 



Formiate of Amyl. 

C"H«0* = C»»H"0,C»HO'. 
Hermann Kopp. (1845.) Ann. Pharm, 55, 1S3. 

Preparation. 6 pts. of dry formiate of soda are distilled with 7 pte. 
of fusel-oil and 6 pte. of oil of vitriol; the layer of liquid below the 
formiate of amyl which haa passed over, dilated with water, whereby an 
additional quantity of the compound ether is separated; and the decanted 
ether washed with aqaeous carbonate of soda, then with water, digested 
over chloride of calcium, and twice rectified, only the more volatile 
portion being collected. 

Properties, Transparent, colourless, thin liquid, of sp. gr. 0*8743 at 
21^, boiling at 16° under a pressure of 27^8''', and having an agreeable 
fruity odour. 

Kopp. 

12 C ' 72 62-07 61'6 

12 H 12 10-35 : 10-5 

4 32 27-58 27*9 

C^WH)* U6 100-00 1000 

The ether quickly turns acid in vessels containing air. 
It dissolves sparingly in water. (Kopp.) 



Chlorofonmate of Amyl, 

C»H"C10* = C»«H»0,C«C10'. 

Cahours. (1847.) iV. Ann. Chim. Phys. 19, 351. 
Medlock. Ann. Pharm. Qd, 217 and 71, 104; also Chem. Soc. Qu. J, 
1, 368 and 2, 252. 

Chlorocarbonate of Amyl, Chlorkohlensaures Amyloxyd, ChlorameUmmyUster. 

Foi'mation and Preparation, h Perchloroxalate of methyl is resolved 
by fusel-oil into hydrochloric acid, oxalate of amyl, and chloroformiate of 
amyl. (Cahours, ix, 177.) — 2. Pure fusel-oil introduced into a flask 
filled with phosgene gas, absorbs it rapidly, with great evolution of heat, 
1 gramme of fusel-oil taking np about a litre of gas. (Medlock.) 

C»»H«02 + 2CC10 « C«H"C10< + HCl. 



CYANIDB OF AMYL. 67 

Properties, — Ve>7 pungent-sinelling liquid, bpiliTijg between 150° and 
160**. (Cahours.) Amber-coloured oil. (Medlock,) 

Decompositiofis. |. Cbloroformiate of apiyl begins to boil at 180^ 
when distilled from a perfectly dry retort; but tbe boiling point qpickly 
rises to 224°, and thence, but slowly, higher, the ether being at the same 
time converted, with evolution of hydrochloric acid, into carbonate of 
amyl (no more forming a solid compound with ammonia), of which both 
the distillate and the residue are then found to consist. (Medlock.) In 
presence of water, the equation is 

C"H"C10< + HO = C"H"0» + C0« + HCl j 

in the absence of water, the carbonate of t^nyl is formed from a pojrtion 
of the cbloroformiate itself; so that in this case a large quantity of charred 
matter remains in the retort. (Medlock.) — 2. It ip^xes with aqueous 
ammonia^ producing intumescence, and the oil which rises to the surface 
solidifies on cooling, in a crystalline mass consisting of carbonate of amyl 
and sal-ammoniac. (Medlock.) 

C"H»C10< + 2NH» = C»NH»0* + NH^Cl (Medlock). 

Valerate of Methyl. 

C»H»0* = C»H»0,C»*»H«0'. 

H. Kopp. (1845.) Ann. Pharm, 55, 185. —Pogg. 72, 287. 

Preparation, 4 pts. of valerate of soda are distilled with 4 pts. of 
wood-spirit and 3 pts. of oil of vitriol, with one cohobatiou; the distillate 
shaken up with milk of lime; repeatedly dehydrated over chloride of cal- 
cium; rectified after decantation thereform; and a^in rectified with a 
fresh receiver, the portion which distils over between 1]4° and 115^, with 
a platinum wire immersed in the liquid, being collected apart. 

Properties. Transparent, colourless liquid of sp. gr. 0*8869 at 15°; 
boiling at 116-2° with platinum wir^ immersed, find h^pyipg ft strong 
aromatic odour like woodnspirit and valerian. (Kopp,) 

Kopp. 

12 C 72 .... 62-07 6lrW 

12 H 12 .... 10-34 10-33 

4 O 32 .... 27-59 2847 

C«H"0* 1]6 .... 100-00 100-00 

Cyanide of Amyl. 

C»NH" = C"H»^C»NH. f 

Balakd. (1844.) iV. Ann. Chim. Phys, 12, 204; also J. pr. CJiem. 

34, 136. 

Fbankland & KoLBE. Ann, PJuirm. 65, 297. 

Bbazibr & GosaLETH. Ann, Pharm, 75, 251. 

Cyanamyl, Cyanmyl<0W, Ether cyanhydramylique. 

Formed: 1. By beating eyonide of potassium with amylosolphaie of 

potassium: 

C«NK + C">H"KO«,260» - C^NH" + «(KO,eO»). 

F 2 



68 AMYLENE: PRIMARY NUCLEUS C»H»o. 

2. Bj heating cyanide of potassium with chloride of amyl, chloride of 
potassium being separated at the same time: 

(?NK + CWH"C1 « C»NH" + KCl. 

3. By heating cyanide of potassium with oxalate of amyl: 

2C2NK + C«H«0« - 2C»2NH" + C*K«08 (Balard). 

An intimate mixture of cyanide of potassium and amylosulphate of 
potassium in equal numbers ot atoms is distilled^ and the distillate shaken 
up several times with water, then dried oyer chloride of calcium, and 
rectified. (Frankland and Kolbe.) 

Thin liquid of sp. gr. 0-806 at 20**; boiling steadily at 146°; having 
a vapour density of 3'335, and a peculiar^ not very unpleasant odour. 
(Frankland & Kolbe.) 

Frankland 
& Kolbe. 

12 C 72 .... 74-23 74-37 

N 14 .... 14-43 

11 H 11 .... 11-34 11-67 



C"NH» 97 .... 100-00 

Vol. Density. 

C-vaponr 12 4*9920 

N-gaa 1 0-9706 

H-gas 11 0-7623 



Vap. of C»«NH".... 2 6-7249 

1 3-3624 

^ Cyanide of amyl is decomposed by boiling with aqueous, and more 
quickly with alcoholic potash, yielding ammonia and caproate of potash: 

C^NH" + 3H0 + KO = C«H»KO< + NH*. 

With potassium, it yields, together with gaseous products, an alkaloid 
corresponding to cyanethiue. (Medlock, Aniu Fharm. 69, 229.) 

It dissolves sparingly in water, and in all proportions in dUsolioL 
(Frankland & Kolbe.) 



Sulphooyanide of Amyl. 

0. Hbnrt. (1849.) N. Ann. Chim, Phys, 25, 246; also N. J. Fharm. 14, 

248; also J. pr. Ckem. 46, 161. 
Medlock. Chem, Soc, Qu, J, 1, 373; Ann, Pkarm. 69, 222. 

Sehwrfelcyanamyl, Schwrfeleyan^mylqfer, Sulfoeyanure d'Amyle. 

Formaiian and Freparation, 1. Crystallized amylosulphate and 
crystallised sulphooyanide of potassium in about equal volumes, are dis- 
tilled together in a large retort with a cooled receiver; the yellow oil 
which passes over separated from the water, dried over chloride of 



ACETATE OF AMYL. 69 

calcium/ and rectified; and this treatment with chloride of calcium and 
rectification repeated several times (Henry): 

CWH"K0^2SO» + C«NKS» = C»NH"S» + 2(KO,SO»). 

2. When an intimate mixture of 2 pts. amjlosulphate of lime and 1 pt. 
of sulphocjanide of potassium — which^ to avoid violent intumescence, 
mu£t be dried as completely as possible — is distilled in a retort of twice 
the capacity of the mixture, there is obtained, after a small quantity of 
water having a very j>eculiar odour has passed over, a yellow oil having 
the same odour. This oil is distilled with water; removed with the 
pipette; dried over chloride of calcium, which withdraws the last quau< 
tities of water with difficulty, and dissolves somewhat abundantly; and 
rectified, the boiling point rising from 150° to 195^, from which point 
upwards the greater part is to be distilled into a fresh receiver. This 
last portion, again subjected to fractional rectification, yields the pure 
sulphocyanide of amyl, boiling at 197". (Medlock.) 

Properties. Thin colourless liquid. (Henry.) Pale yellow oil, boiling 

steadily at 197°. (Medlock.) it begins to boil at 170*>, the greater portion 
passing over between 195° and 210**, but the remainder not till the temperature rises to 
260**; the oil which passes over after repeated rectification between 210° and 240^ has u 
density of 0-905 at 20". (Henry.) Has a pungent alliaceous odour. (Henry.) 

Henry. Medlock. 

12 C 72 .... 55-81 .... 56-86 .... 56-69 

N 14 .... 10-85 .... 10-84 

11 H 11 .... 8-52 .... 8-81 .... 8-95 

2 S 32 .... 24-82 

CWNRMS? 129 .... 100-00 

The ether analysed by Henry was coUected between 195** and 210'. 

Decomposition. Moderately strong nitric acid acts violently on the 
compound, giving off nitrous vapours, nitrogen gas and carbonic acid, 
and forming amylosulphurous acid together with a small quantity of 
sulphuric acid. (Henry; Medlock.) 



Acetate of Amyl. 
C"ff *0* = Ci»H"0,C*H»0». 

Cahoitrs. (1840.) Ann. Chim. Phys. 75, 193; also Ann. Phamt. 37, 167; 

also J. pr. Chem. 22, 171. 
Hermann Kopp. Ann. Pharm. 55, 187. 

Amy He Aettate, Essiffsaures Amyloxyd^ Eiiiy-myletter, Acetate d* Amy line. — 
The so-called fiear oil used in perfumery consiata of this ether. (A. W. Hofmann, 
AftH. Phwm. 81 1 87*) 

FomuUion. This compouDd is produced even by leaving a mixture of 
fusel- oil and moderately strong acetic acid to stand for several days. 
(Dobereiner.) 



70 AMYLENBl IMIIMAUY NUCLEUS C'"il'«. 

PrepdrtUioii. 2 pts. of ftc^iaie of botash ^fe distilled witli 1 pL bf fusel- 
oil and 1 pt. oil of vitriol; the distilllite washed with water coDtaiuing 
potash, dried over chloride of oalciam, and rectified over oxide of lead 
(Cahours.)— 2. The distillate obtained from 3 pts. of dehydrated acetate 
of l^ad, 1 ft of fasel-oil and 1 part oil of vitriol, is shaken up with milk 
of liraO) aehtdrated over chloride of caloinm and rectified, the small 
portion wkioh paaaes oVer below 133'' and becomes turbid when mixed 
with wateri lihd that also which distils above 140°, being set aside. In the 
nstoii thtf^ remAina a turbid liquid, amoantio^ to -1^ of tlie whole, whieh depottte 
cryatalline spangles ahd becomes olear. (Kopp.) 

Properties, Transparent^ colourless liquid, lighter than water (Ca- 
hours), of sp. gr. 0-8572 at 21°. (Kopp.) Boils at 125"* (Cahours); with 
a platinum- wire immersed in it^ it bous constantly at 133*3° under a 
pressure of 37" 8"'. ^Kopp.) Vapour density = 4*458. Odour, ethereal 
and aromatic, somewnat lik^ that of acetate of ethyL (Cahotura) 

Cabovrs. Kopp. 

14 C 64 .... 64'6l .... 64-4:^ .... 64-08 

14 tt 14 .... 10-77 .... 10-68 .... 10-98 

4 32 .... 24-62 .... 24*85 .... 24-94 

--It- • ' • • •• — ' — 

C"HWO* :.;...,. 180 .... 100-00 .... 100-00 .... 100-00 

Vol. Density. 

C-Tapour 14 .... 5-8240 

H-gas 14 .... 0-9702 

O-gas 2 .... 2-2186 

Vapour of Amyltc Acetate ...» 2 .... 9'0128 

1 .... 4-5064 

Decompwitione. li Well dried acetate of amyl absorbs chlorine gas 
passed through it, becoming heated thereby, and, when treated with 
chlorine at 100°, as long as hydrochlorio acid continues to escape, is con- 
verted into chloracetate of amyl, C^^C^H^^O^ which^ by the action of 
chlorine in sunshine, is converted into a higher chlorine-compound. — 
2. It is not coloured by oil of vitriol in the cold, but when heated there- 
with, it becomes redclish yellow, then black, and gives off sulphurous 
acid- — 3. It is decomposed very slowly by aqueous, but quickly by alco- 
holic potash, into acetate of potash and fusel-oil. (Cahours.) 

Comhinatione, Insoluble in Wafer, but dissolves in alcohol, ether, and 
fujselroil, (Cahours.) 



Chloracetate of AmyL 

C"C1'H»0* = C^°H"0,C*CPHO». 

CABotJRB. (1840.) Ann, CJdm. Phys. 79, 193. 

ChlorhalHgea essigaaurpt Amyloxyd, Chloressigmylester, Acetate d* Amylene ehlori, 

rt^aration. Dry chlorine gas is passed through well dried acetate 
of amyl, first at the ordinary temperature, then at 100°, as lon^ ad 



VALERATE OF ETHYL. 71 

hydrochloric acid gas continues to be evolred ; and the product washed 
with aqueous carbonate of soda, then with a large quantity of pure water, 
and dried in vacuo over oil of yitriol. 

Properties, Thin colourless oil, heaviei^ than wateif and haying an 
agreeable odour. 

Cahoun. 
14 C 84-0 .... 42-26 .... 4226 

2 CI 70-8 M.. 35-61 .... 36-29 

12 H 12-0 .... 6-03 .... 6-07 

4 O 32-0 .... 1610 ... 16-38 






C»*Cl«Hi20^ 198-8 .... 10000 .... 100*00 

Decompositions. 1. Chloracetate of amyl assumes a strong yellow 
colour at 150°, and decomposes completely when distilled. — 2. When 
exposed for some time to the sun in a bottle filled with chlorine-gas, it 
does not thicken, but deposits small needles, and in the end is probably 
converted wholly into C"C1"0*. ^Cahours.) 

It is insoluble in water, but dissolves in alcohol and still more readily 
in ether. (Cahours.) 



Valerate of Ethyl. 

(?*H"0* = C*H»0,C"H»0>. 

Otto. (1838.) Ann, Pliarm, 25, 62; 27, 225. 
H. Kopp. Ann. Fharm. 55, 187. 

Valsrianie ethwr, Baldrian-mnetter, 

Preparation, 8 pts. of valerate of soda are distilled with 10 pts. of 
88 per cent, alcohol and 5 pts. oil of vitriol; the resulting valerate of 
ethyl, a portion of which separates from the distillate only on addition 
of water, washed with dilute carbonate of soda, then with pure water, 
dehydrated over chloride of calcium, decanted, and distilled with a 
platinum-wire immersed in it; and the portion which distils at 133^ 
collected apart. (Kopp.) 

Properties, Transparent, colourless liquid, of sp. gr. 0*894 at 13° 
(Otto); 0-8659 at 18° (Kopp); 0869 at 14* (Bertlielot, N^, Ann, Chim, 
Phtjs, 41, 254); 0870 at 135°. rDelffs.) Boils at 133;5° (Otto); at 
]33'2°, with platinum-wire immersea (Kopp); at 131*5°, with the bar. at 
325*7° mm. (Delffs); between 133^ and 134°. (Berthelot.) Vapour- 
density 4*558. Odour penetrating, like fruit and valerian. (Otto.) 
Index of refraation for the red ray, 1 -3904. (Delis, N. Jakrb, Pkarm, 

1, 1.) 

Otto. Kopp. Berthelot. 

14 C 84 .... 64*61 .... 64-84 .... 6400 .... 64*2 

14 H 14 .... 10*77 .... 10-79 .... 1097 .... 110 

4 O 32 .... 24-62 .... 24-37 .... 25-03 .... 24-8 

C"U"0* .... 13D .... lUO 00 .... 10000 .... lOD-00 .... 100-0 



72 AMYLENE: PRIMARY NUCLEUS C»H»». 

Vol. Density. 

C-vapoar 14 .... 5-8240 

H.gas 14 .... 0-9702 

O-gas 2 .... 2-2186 

Vapour of Valerianic ether 2 .... 90128 

1 .... 4-5064 

Berthelot's product was prepared with Talerianic acid obtuned from dolphin-oil. 

Decompodttans. Strong ammonia decomposes valerate of ethjl in a 
few weeks, into yaleramide and alcohol. (Damas, Malagati & Leblanc; 
Dessaignes & Chantard): 

C"H"0* + NH» « CWNH»02 + C^H«0». 



Oxalate of Amyl. 

C«*H»0« = 2C»^H»0,C*0*. 

Balard. (1844.) iV. Ann, Ckim, Pkys, 12, 309; also J. pr, Chan, 

34, 137. 
Cahoubb. N. Ann, Ckim. Phys, 19, 351. 



• 



OxdUaureM Amyloxydy Oxal-myletter, Biker oxalamylique. 

Preparation. 1. When fusel- oil is heated with a large excess of 
crystallised oxalic acid, two layers are formed, the lower consisting of 
aqueous oxalic acid, and the upper of an oil which smells like bugs, and 
deposits oxalic acid on cooling. On distilling this oil, collecting apart 
the portion which goes over at 262% and rectifying this portion with the 
same precaution, the pure oxalate of amyl is obtained. ^Balard.)-— 
2. When perchloroxalate of methyl (ix, 176), is decomposed oy fusel'oil, 
oxalate of amyl is obtained together with the perchloro-formiate (p. ) 
(Cahours.) 

Properties. Colourless liquid boiling at 262° (260*^ according to 
Cahours), having a vapour-density of 8*4, and a strong odour of bugs. 
(Balard.) 

Balard. Cahoars. 

24 C 144 .... 62-61 .... 62-4 .... 62-30 

22 H 22 .... 9-56 .... 9-7 .... 9-56 

8 O 64 .... 27-83 .... 27-9 .... 28-14 

C»*H«0» 230 .... 100-00 .... 100-0 .... 100*00 

Decompositions, 1 . Oxalate of amyl is decomposed by water and 
more quickly by aqueous fixed alkalis, into fusel-oil and oxalic acid. — 

2. With dry ammoniacal gas, it yields oxamylene and fusel-oil : 

C«H«09 + NH« = CMNH"0« + CWH>«0«. 

3. With aqueous ammonia it is converted into oxamide and fusel-oil ; 

C?<H«0» + 2NH» « C*N«H*0< + 2CWH»K)», 



AM7L0XALTC ACID* 73 

4. With cyanide of potassiam, it yielda oxalate of potash and cyanide of 
amyl : 

C«*H«0« + 2C«NK = C*KH)« + 2C'«NH" (Balard). 



Amylozalic Acid. 

C"H"(y = C«'H"0»,O0^ 

Balard. (1844.) N. Aniu Chim. Phys. 12, 309; also «7. pr. Chem, 
34, 137. 

OxamyHe acid, OxdUanylic acid. 

When the oil ohtained by heating fasel-oil with excess of cr3r8talli8ed 
oxalic acid {vid. tup.), is saturated with carbonate of lime after being sepa- 
rated from the watery layer, the liquid yields by eyaporation, crystallised 
amyloxalate of lime, from which the other salts may be prepared. 

AmyhxalaJU of Potcuik, — Obtained by precipitating the lime-salt with 
carbonate of potash, and eraporating the filtrate. Needles nnctuous to 
the touch and having a pearly lustre. 

Amyloxalate of Lime* — Rectangular laminae, which, when heated to 100° 
in a current of air, or after solution in water, are resolved into fusel-oil, 
oxalate of lime and free oxalic acid; they dissolve more readily in hot 
than in cold water. 

Cryttah. Balard. 

CaO 28 .... 14-21 18-9 

14 C 84 .... 42-63 41-8 

11 H 11 .... 5-59 5.4 

7 56 .... 28-43 

2 HO 18 .... 9-14 

C»<H"CaO» + 2Aq 197 .... 100-00 

Amyloxalate of Silver. — By mixing the limensalt with a solution of 
silver, the silver-salt is obtained in anhydrous laminsd, which are 
unctuous to the touch, have a pearly lustre, dissolve sparingly in water, 
and decompose by keepiuff into oxalate of silver, free oxalic acid, and a 
substance which cannot be fusel-oil, as there is not enough water to 
produce it. (Balard.) 

CrystaU, Balard. 

14 C..., 84 .... 31-46 .... 30-2 

11 H 11 .... 4-12 .... 3-9 

Ag 108 .... 40-45 .... 39-6 

8 O 64 .... 23-97 .... 26-3 

C"H"AgO» ., 267 .... 100-00 ...• lOO'O 



74 AMYLENK: PRIMARY NUCLEUS Om^. 



Allophanate of Amyl. f 

LiEBiG. (1846.) Ann. Fharm. 57, 128. 
ScHLiEPER. Ann. Fharm, 59, 23* 
RiECKHER. Jahrh. pr, Fharm. 14, 1. 
WuBTZ. Compt. rend. 29, 186. 

Cyanurate qf Amyl, Cyatutmret Amyloxyd, AHopkan-mylefti^, 

Formation and Freparation. 1. When the vapour of cyanic acid 
eyolved from heated cyanuric acid is passed into anhydrous fusel-oil, 
crystals of this compound ether are obtained and may be purified by 
crystallisation from water. (Liebig.^ Fusel-oil absorbs the yapour of 
cyanic acid, with great evolution oi heat, becomes viscid, and deposits 
laminsB, in consequence of which it solidifies to a stiff magma on coolinff. 
This mass is boiled with water, which is renewed from time to time, till 
the odour of fusel-oil is no longer perceptible, then filtered from the 
cyamelide (ix, 462^, into which part of the cyanic acid has been converted, 
and left to crystallise by cooling. (Schlieper.) — 2. Cyanate of potash 
is distilled with amylosulphate of potash. (Wurt2.) [Is not the addition of 
Bolpharic acid necessary ?] 

Fropert%€8. Snow-white, nacteous, bulky scales, unctuous to the touch 
(Schlieper); deceptirely like leucin. (Liebig.) Melts when gently 
heated, and sublimes between two watch-glasses, even at 100^, in shining 
laminsB. Destitute of taste and smell ; neutral to vegetable colours. 
(Schlieper.) 

Schlieper. Rieekher. 
14 C 84 .... 49-28 .... 48*62 

2 N 28 .... 16-09 .... 16-36 .... 18*08 

14 H 14 .... 805 .... 808 

6 48 .... 27-58 .... 26*94 



h f 



CMNJH"0« 174 .... 10000 .... 100-00 

Sehlieper reg^ards the body as a compound of 3 At. amylic ether with 2 At. 
cyannriG aOid » aCi^H^^O -¥ 2C"N*H*0' $ bat its analogy with allophanate of ethyl 
(ix, 268) is quite unmistakabls. 

DecomposiUoM. 1. The ether when heated above its melting point, 
boils, gives off a large quantity of amylic alcohol, and leaves a crystalline 
residue of pure cyanuric acid : 

3C"NniMO« « 3CWH«02 + 2C«N»H30«. 

2. When distilled with aqueous alkalis, it readily gives off fusel-oil. 
(Schlieper.) By hot potash-solution it is converted into carbonate of 
potash, amylamine [and ammonia]. (Wurtz): 

CHN«H"0« + 4KO + 2H0 » 4(K0,C0«) + C»ONH» + NH». 

It is not decomposed by chlorine, bromine, nitric acid, sulphuretted 
hydrogen, or ammonia. (Schlieper.) 



MONOVALERIN. 75 

Combinations. The ether is not wetted or dissolved by cold water, 
bat dissolves readily in hot water; the saturated solution becomes covered 
with an irridescent film, and on cooling deposits the ether in large flakes. 
and needles, which assame the scaly aspect when dry. (Schlieper.) 

The aqueous solution does not precipitate any metallic salt. 
(Schlieper.) 

AUophanate of amyl dissolves with tolerable facility in vinic ether 
(whereby it is distinguished from leucin) (Liebig); also in alcohol, whence 
it is precipitated by water. (Schlieper.) 



T Monovalerin. 

Berthelot. iV. Ann, Chim. Fhys. 41, 254. 
MoTiophocenin* 

Formed by the action of yalerianio acid upon glycerine in excess at a 
high temperature: 

CWH»*0* + CHW = C»H»«0» + 2H0. 

A mixture of the strongest valerianic acid and excess of glycerine is 
heated to 200° in a sealed tube for three hours; the mixture when cold, 
supersatuhited with carbonate of potash; a stnall quantity of caustic potash 
then added; the liquid shaken up with animal charco&l; the filtrate evapo- 
rated over the water-bath; and the residue dried in vacuo on a strongly 
heated sand-bath. 

Oily, neutral, ddorous liquid, of sp. gr. 1*100 at 16'. 





... 96 
... 16 


... 54-5 .... 
.... 9-1 .... 
.... 36*4 .... 




Bertbelot. 


16 C 

16 H 


52-2 

91 

38-7 


.... 53-3 .... 52-6 
.... 9-2 .... 8-6 


8 O 


... 64 


.... 37*5 .... 38*8 






* 


CWH»«08 


.... 176 


.... 1000 ... 


1000 


.... 1000 .... 1000 



Metameric with butyric acid. 

Decomposed in a few hours at ordinary temperatures by hydrochloric 
acid and alcohol, yielding glycerine and valerate of ethyl. 

1 vol. monovalerin treated with \ vol. water forms a limpid mixture, 
another | vol. water causes the valerin to separate out in a mass; 8 or 10 
vol. water produce the same precipitation. With 100 times its volume 
of water, monb valerin forms a solution or rather an emulsion. 

\ valerin is also obtained by heating a mlxtmre of glycerine and valeriahie acid to 
IOC* in an atmosphere of hydrochloric acid gas. The product contains chlorhydrin. 
(Berthelot.) 



76 AMYLENE: PHIMARY NUCLEUS C"H^ 

% Bivalerin. 

Berthelot. i\r. Ann. Chim, Phys, 41 , 255. 

JHvalerin, Diphocenin, 

Prepared by heating to 275^ a mixture of glycerine and yalerianic 
acid slightly diluted with water, and treating the product as in the 
preparation of monovalerin. 

[2CMH>«0* + C«H80« - C»IP*OW + 4HO]. 

Oily neutral liquid, of sp. gr. 1*059 at 16^ Has a disagreeable odour 
like that of fish-oil, and a bitter aromatic taste. Solidifies at— 40^ 
becoming semi-soft but retaining its transparency. 

Berthelot. 

26 C 156 .... 60-0 .... 55-6 .... 55-2 

24 H 24 .... 9-2 .... 9*9 .... 95 

10 O 80 .... 30-8 .... 34-5 .... 35-3 

C»H**OW .... 260 .... 100-0 .... 100-0 .... 100-0 

[Berthelot gives the formala C^H^^O^, which certainly agrees mnch better with 
his analysis, requiring 56*1 C and 9*4 H. The formula above given is however mnch 
more probable (see iz, 491) ; most probably the substance analysed by Berthelot was 
impure.] 

Bivalerin is decomposed by baryta, yielding valerate of baryta, — 
Treated with hydrochloric acid and alcohol at ordinary temperatures, it is 
decomposed, yielding glycerine and valerate of ethyl. — The same pro- 
ducts of decomposition are obtained by heating a solution of bivalerin in 
alcohol to 100° for 63 hours. The formation of valerianic ether takes place 
even on exposing the alcoholic solution to the air at ordinary tempera- 
tures; in a closed vessel, only traces of decomposition are observed. — 
Water, acetic acid and aqueous hydrochloric acid, heated to 100° with 
bivalerin for 63 hours, decompose it with reproduction of valerianic acid; 
with water, this effect takes place in a slight degree only; but with hydro- 
chloric acid, it is considerable. — Ammonia slowly changes bivalerin into 
crystallised valeramide. 

1 vol. bivalerin and \ vol. water do not form a limpid mixture; 
8 to 10 vol. water form a very instable emulsion from which the bivalerin 
separates in a mass, which is not dissolved, even by the gradual addition 
of a large quantity of water. (Berthelot.) 

IT Trivalerm, 

Berthelot. N. Ann, Chim. Phy$, 41, 257i 

Triphocenin^ 



DELPHININ. 77 

Obtained by heating to 220° for eight hours^ a mixture of bivalerin 
with 8 to 10 times its weight of valerianic acid: 

3CWH»0* + C«HH)« = C»H»0>2 + 6HO. 

Oily, neutral liquid having a faint disa^eeable odour. Treated at 
ordinary temperatures with hydrochloric acid and alcohol, it is resolved 
in two days into glycerine and valerate of ethyl. — It is insoluble in 
water^ but soluble in alcohol and in ether. 

Berthelot. 

36 C 216 .... 62-8 .... 61-6 

32 H 32 .... 9-3 .... 90 

12 O 96 .... 27-9 .... 29-4 

C?»H«0»2 344 .... 100-0 .... 1000 

The Valerius, when exposed to the air, become completely acidified in 
the course of a {ew weeks, acquiring the odour of valerianic acid. The 
elimination of this acid is not due to oxidation; for bivalerin and mono- 
valerin placed in an atmosphere of moist oxygen for 2^ months, absorb 
but very small quantities of it; it is only when the liquid is in contact 
with brass filings, that the absorption becomes perceptible. It then 
amounts to about 2 per cent of the weight of the oil. (Berthelot) IT. 



Delphinin or Fhocenin* 
C«H«0^* ? = e'H*0»,4C"H*0». ? 

Chetbeul. (1818.) Ann. Chim, Phys, 22,^374. — Recherehes mr Ui carpi 
groi. 190, 287 and 467. 

Baldria^fett, Delphi^fett, Phocinine. — Found in the oil of Delpkinus 
globicepB, D, phoccea and D, marginaiiu; not yet obtained in the pure 
state, the olein not having been completely separated. 

Preparation, 100 pts. of dolphin-oil are dissolved in 90 pts. of warm 
alcohol of sp. gr. 0*797; the solution decanted from the oil which is pre- 
cipitated on cooling, and distilled with water; the oil which remains in 
the retort, and consists of a mixture of delphinin and olein, separated 
from the watery liquid, and treated with cold dilute alcohol; and the 
alcohol evaporated, after the solution has been separated from the nndis- 
solved olein. 

Properties. Oil very mobile at 17°; of sp. gr. 0-954 [0-948 (Berthe- 
lot)]; having a faint, peculiar, somewhat ethereal odour like that of vale- 
rianic acid; not reddening litmus. [Boiling point 258® (Berthelot).] 

Decompositions. 1. The alcoholic solution diluted with a large 
quantity of water, and distilled, leaves delphinin which reddens litmus, 
from containing free valerianic acid. The fat, when exposed to warm 
air, likewise acquires the power of reddening litmus, and a strong 
odour proceediufi; from the liberate<^ valerianic acid. — 2. Delphinin 
heated to 100° with an equal quantity of oil of vitriol, and then left to 
itself, gives off, after a week, the odour of valerianic and sulphurous acid; 



78 AMYLENE: PRIMARY NUCI.EUS C"H". 

water added to it takes up salphoric, sulphogljoeric, i^nd valerianio acid, 
and glycerine, and leaves an oily mixture of valerianic acid, oleic acid, 
and a small quantity of unsaponified fat. — 3. A hundred parts of 
delphinin saponified with potash, yield 36 pts. Vj^erianic acid, 59 pt& 
oleic acid, and 15 pts. of glycerine. 

If. 100 pts. of the oil of the common porpoise (Delphinus phoccea) 
saponified with baryta, yielded 82*2 pts. of fixed fatty acids, 16 pts. 
phocenate (valerate) of baryta, and 14 glycerine, or 6' 7 pts. glycerine 
to 100 pts. valerianic acid (C^^'H^^'O*). The same oil treated with 
alcohol yielded successively three oils, containing respectively 4*4 pts., 
4*4 pts. and 51 pts. glycerine to 10 pts. valerianic acid. The first of these 
three oils when again treated with alcohol, yielded a new liquid (phocenin^ 
containing 2 '7 pts. glycerine to 10 pts. of valerianic acid. (Chevreul.) 
The oil of Delphinus globiceps was found to contain, besides fixed fatty 
acids and ethal, 5*9 pts. glycerine to 10*0 valerianic acid. Now for 
10 pts. of valerianic acid, monovalerin contains 9'0 pts., bivalerin 
4*5 pts., and trivalerin 3*0 pts. of glycerine. Hence it appears that 
phocenin is intermediate in composition between the artificial valerins, 
and may therefore be regarded as a mixture of them — ^a conclusion 
further warranted by its separation into valeric acid and glycerine by 
saponification. (Berthelot.) f. 

CoTnhinatioiu. Dissolves abundantly in hot alcohol. (Chevreul.) 



Valerone. 

LbwiG. (1837.) Fogg. 42, 212. 

Preparation. Valerianic aoi4 is cautiously heated in a distillatory 
apparatus with excess of lime, and the distillate purified by Motification 
over fresh lime. 

Properties, ColourloAS, veiy thin liquid, lighter than water, boiling 
much below 100°, having an agreeably ethereal odi)nr like valerianic acid, 
a cooling etheroal taste, and perfectly neutral 

Lowig. 

18 C 108 .... 76-06 .... 75-36 

18 H 18 .... 12-67 .... 12-40 

2 O 16 .... 11-27 .... 12-24 

I.I 

CiSH«0' 142 .... 100-00 ,... 100-00 

Decompositions. 1. Valerone burns with a very smoky flame. — 
2. It becomes less heated than acetone by contact with potassium, and 
the mass formed therewith separates, on addition of water, an oil which 
exhibits similar properties to that obtained with acetone (ix, 15, 16). 
(Lowig.) 

Chancel (Compt. rend. 21, 905) regards LSwig's valerone as a mixture of a very 
small quantity of valerone with a very large quantity of valeraK 



Al^lTtOMAUC ACID. 79 

^ Valeracetone. 

Williamson. Chem, Soc. Qtl J, 4, 238. 

Formed by distilling a mixture of acetate of soda [or potash] and 
valerate of potash in equal numbers of atoms: 

C^H'KO* + C^H^KO^ = C«H"0« + 2(K0,C0*). 

The salts were dissolved in water, and evaporated to dryness, the mixture 
distilled in a retort; the oily di<«tillate shaken up with aqueous potash to 
remove undecomposed acids, and after separation from the potash, distilled 
with the thermometer. By uniting the products of several distillations, a 
liquid was obtained, boiling with perfect regularity at 120^, and consti- 
tuting nearly two-thirds of the entire distillate: 

Williamson. 

12 C ya .... 72 .... 71-38 

12 H 12 .... 12 .M. 1212 

2 16 .... 16 .... 16-50 

CWH«0« 100 .... 100 .... 100-00 

[May be regarded w ^jjs | or ^^i^ |]. 



1 Amylomalic Acid. 

£. Breunlin. Ann. Fharm. 91, 323. 
Mtiamylic add, AmyldpfeUaure. 

When 1 At. fusel-oil and i At malic acid are digested together for 
some time at 120°, the malic acid gradually dissolves; the odour of the 
fusel-oil disappears; and the product, which is a viscid syrup while hot, 
solidifies on cooling in a white crystalline mass of the hydrprted acid, 
which is soft and unctuous to the touch, melts at a gentle heat, and dis- 
solves readily in water, alcohol and ether. 

Amylomalate of Ammonia. Obtained by decomposing the lime-salt 
with carbonate of ammonia. Crystallizes only from a dilute alcoholic 
solution, in long needles united in concentric groups and having a 
diamond lustre. 

Brennlin. 

NH^O 26 .... 11-76 .... 11-74 

C»0H"0 79 .... S6-75 

C*H*0« 116 .... 62 49 



l-MI 



NH^O.CWU"0,C8H*08 .... 221 .... 100-00 



80 AMYLENE. PRIMARY NUCLEUS C>«H**. 

The Potash and Sodorsalts do not crystallise, either from aqueous or 
from alcoholic solutions. 

AmplomcUate of Baryta, — A solution of amlyomalic acid saturated 
i¥ith carbonate of baryta, then filtered and evaporated, ultimately prields 
a thick, uncrystallisable syrup. On mixing a dilute aqueous solution of 
this 83rrup with alcohol, a bulky white precipitate is formed, which, after 
filtration, washing with alcohol, pressing, and drying in vacuo over oil of 
vitriol, becomes hard and brittle and may be pulverised. At lOO'' it 
melts into a resinous mass and obstinately retains water. After drying 
for some time at 100°, it ^ve by analysis 48 '3 p. c. BaO, a quantity not 
agreeing with the formula BaO,C*«H"0,C'»H*0", which requires 28 26 
p. c. BaO. — The aqueous solution of the salt heated with potash, gave 
off fusel-oil in considerable quantity. 

AmylomalcUe of Lime, — When a warm dilute aqueous solution of 
amylomalic acid is saturated with chalk, and filtered hot, the filtrate 
solidifies on cooling iu a white laminated crystalline mass, which may be 
purified by recrystallisation and pressure between bibulous paper. When 
dried in vacuo over oil of vitriol, it ^ves off water, and acquires a fatty 
lustre. At 100° it melts into a thick syrup. 

Dried in vticno over oil qfvitrioL Breunlin. 

CaO 28 .... 12-07 .... 12-10 

18 C 108 .... 46-55 .... 46-06 

16 H 16 .... 6-89 .... 7-42 

10 O 88 .... 34-49 .... 34*42 

CaO,CWH"0,C"H<08 + Aq .... 240 .... 100-00 .... 100-00 

The UadrsdU is insoluble in water, and melts in hot water like the 
malate. 

The other salts of amylomalic acid are all soluble in water; they do 
not give any conspicuous reactions. (Breunlin.) %, 



Amylotartaric Acid. 

G«H*«0" = C^«»H»0»,C*H*0^° = C^«H"0,HO,C*.H*0'^ 

Balard (1844.) N, Ann. Chim, Phys, 12, 309; also J, pr. Chem. 

34, 141. 
Bbeunlin. Ann. Pharm, 91, 314. 

gp Tartramylie acid, AmyHartereaure, Amylweimaure, 

Preparation. 1. When fusel-oil is distilled with tartaric acid, a 
portion of the fusel-oil itself first passes over, then an acid and an ethereal 
product, and in the retort there remains a liquid which is syrupy after 
cooling, and characterised by intolerable bitterness. This liquid deposits, 
in the course of 24 hours, a white substance which does not behave like 
amylotartaric acid; the solution yields with carbonate of lime, unctuous, 
nacreous laminsB, which dissolve very abundantly in water, forming a 
solution from which a concentrated solution of nitrate of silver throws 
down the sparingly soluble silver-salt. (Balard.) — % 2. When 150 pts. 



AMYLOTAftTAKIC ACID. 81 

of finely pnlveriied crystallised tartarie aeid are digested for several 
days at aboat 130° with 88 pts. of rectified amvlic alcohol, the tartarie 
acid gradaally dissolves, the odoar of the alcohol disappears, and a 
syrupy, yellowish liquid is formed, which by slow coolinff solidifies in 
nnctuous crystals nnited in warty masses. — These crystals nave scarcely 
any odonr of fusel-oil, but an extremely bitter taste. They melt at a 
gentle heat; dissolve very sparingly iu a small quantity of water; and 
a larger quantity of water added to the solution separates the acid in 
oily drops.. ^Brettnlin.) 

The Amylotartrates are for the most part soluble in water. Most of 
them remain unaltered when their aqueous solutions are boiled, bnt they 
decompose when dried at 100^ (Brennlin.) Their formula is G^°H"MOV 
C«H*0''> or MO, 0^»H»0, CWO". 

Amylotarirate of Potash, — By decomposing the bai^tarsalt, hydrated 
or anhydrous, with an aqueous solution of carbonate of potash, a filtrate 
is obtained which, on evaporation, and cooling, yields a white crystal- 
line saline mass, easily pqrified by re-crystaUisatioo. Gives off its 
water of cnrstnllisation at 100°, and acquires a fatty lustre; the dry mass 
is with diffaculty wetted by water. The crystals dissolve sparingly in 
cold, readily in ooiling water. (Brennlin,) 

Ji^ydroKf, BreunUn. 

KO 47-2 ,.., 18-J8 .... 18-14 

a«H"0 790 .... 80C0 

C«H<OW 1320 ..„ 5112 

C»H»»KOS,C8H*OW... 268-2 .... 100-00 

Hydrated, Brennlin. 

•CiouiiKO«,(?H<0» 258-2 .... 9347 .... 6-34 

2 HO 180 .... 6*53 

CWH"K0«,C8H*0" + 2 Aq. 2762 .... 100-00 

Amylotarirate of Soda. — Prepared like the potash-salt. The concen- 
trated eolation left to stand for aome time in vaono over oil of vitriol 
deposits soft no<1alar erystf^s, which are soluble in watar> deoomposa at 
100^ and are difficult to recrystallise. (Brennlin.) 

Dried i» vacuo, Bieanllii. 

NaO 31-2 .... 12-88 .... 13*88 

CM>H"0 79-0 .... 32-62 

CH^Oi^ 1320 .... 54-40 



••** 



C«»H"NaO«,C»H<0» 242-2 .... 10000 

The ezoesi of lodft arises from contaiqlnation of the salt tvUh carbonate of soda, 
an excels of which waa used to d^oonpoae the baryta-salt. 



AmylotartraU of Baryta,^-^. Anhydrous* — When the aqueous solu- 
tion of the acid is saturated while warm with carbonate of baryta, a 
thick viscid scum forms on the surface, containing amylotartrate of Miryta, 
together with tartrate and carbonate. This substance, after beiuii^ washed 
with water^ is digested in hot ^cobol which dissolves the amylotartrate. 
The solution does not yield any crystals, but on adding water to it, the 

VOL. XI. o 



82 amylene: primary nucleus c"h". 

salt ia precipitated in white amorphous flakes^ which melt into a resinous 
mass at 100 . (Breunlin.) 

Dried at lOO"". Breunlin. 

BaO 76-6 .... 2663 26-43 

C>»HiiO 79-0 .... 27-47 

C8H<0»o 132-0 .... 45-90 

C»0H"BaO«,C«H*OW.... 287*6 .... 10000 
This amorphous salt could not be converted into the crystallised salt b. 

h. Hydrated. — The aqueous solution obtained by neutralising amylo- 
tartaric acid with carbonate of bar3rta, yields, when filtered and concen- 
trated, colourless, nacreous, crystalline lamiuaB, which acquire a fatty 
lustre and become dull when dried at a gentle heat, and are decomposed 
at 100^ (Breunlin.) 

Breunlin. 

BaO 76-6 .... 25-07 .... 25-45 

18 C 108-0 .... 35-34 .... 35-29 

17 H 170 .... 5-56 .... 5-41 

13 O 1040 .... 3403 .... 33-85 

CWH»BaO*,C«H<OW + 2Aq .... 3056 .... 10000 .... 10000 

Amylotartrate of Lime, — By mixing an alcoholic solution of the 
amorphous anhydrous baryta-salt with dilute sulphuric acid, neutralising 
thu Ciolutiou with carbonate of lime while water is gradually added, an:l 
evaporating the filtrate, first over the water-bath, then over oil of yitriol, 
a friable saline mass is obtained, which dissolves readily in water, and is 
not decomposed at 100°. (Breunlin.) 

Breunlin. 

CaO 28 .... 11-72 11-85 

C^H"© 79 .... 33-05 

CSH^O^o 132 .... 55-23 

C»0H"CaO2,(?H*O» 239 .... 10000 

Amylotartrate of Lead, — A solution of the potash-salt mixed with 
acetate of lead, forms a bulky white precipitate very easy to filter and 
wash. After drying at 100°, it yielded 52 p. c. PbO; whereas the 
formula C"H"PbO^C»H*Oi° requires only 34-37 p. c; hence the salt 
obtained as above must be either a basic salt or a mixture of several 
salts. (Breunlin.) 

Amylotartrate of Silver. — When a hot concentrated solution of 
amylotartrate of potash is mixed with nitrate of silver, the liquid on cooling 
yields needles united in tufts and having a diamond lustre; they may be 
purified by washing with a small quantity of water and pressing between 
filtering paper. (Breunlin.) IT. Balard precipitates the lime-salt with 
nitrate of silver (p. 80). 

Balard. Breunlin. 

18 C 108 .... 33-03 .... 32-6 32-5 

15 H 15 .... 4-59 .... 4-6 

Ag 108 .... 3303 .... 32-5 

12 96 .... 29-35 .... 303 

C»H»AgO»... 327 .... 100-00 .... 1000 



PYROTARTARIC AGID. 83 



Valerate of Amyl. 

(?«H»0* = C«^H"0,C'»fl»0». 

Balard. (1844.) Ann, Ckim. Phys. 12, 315 j also J, pr. Cliem. 34, 143. 
Trautwein. Bepert. 91, 12. 

Baldriofi'mylester, Ether vcUeriamylique. — First obtained by Dumas and Stas, bat 
regarded by them as valeraldide (p. 17), which is isomeric with it — ^The so-called 
Afple oil used in perfumery consists of this compound. (Hofmann, Ann. Pharm, 
81, 87.) 

Formation and Preparaiwn. 1. By distilling fusel-oil with valerianic 
acid. (Balard.) — 2. By adding to a cold-saturated solution of bichromate 
of potash, first oil of vitriol, then fusel-oil. (Dumas & Stas, Balard.) 

Properties, Oily liquid, which boils at 196^, and has a vapour-density 
of 6-17. (Balard.) 

Dumas & Stas. 



20 C 

20 H 


120 

20 


.... 69-7;^ 
.... 11-63 
.... 18-60 


70-07 

11*60 


4 O 


32 


18*33 








C^H'^O* 

C-vapour .... 
li.ffas 


172 


.... 10000 

Vol. 

. 20 

. 20 

. 2 


10000 

Density. 
8-3200 
1*3860 


O-gas 


• •••••■■a *>«t«»l 


2*2186 


Vapour of C»H«0« ... 


. 2 


11*9246 
6-9623 



Decompositions. When valerate of amyl is distilled with chromate of 
potash and sulphuric acid, part of it distils over unaltered, while the 
remainder is converted by oxidation into valerianic acid. (Trautwein). — 
2. With aqueous potash, it yields valerianic acid and fusel-oil. (Balard.) 

Combinations, The ether dissolves phosphorus and iodine in large 
quantity, but no sulphur even at the boiling heat. (Trautwein.) 
It dissolves a few resins. (Trautwein.) 



Oxygen-nucletis, C*®H®0'* 

Fyrotartaric Acid, 

V. Rose. N. Oehl. 3, 598. 

FouRCROY & Vauquelin. Ann, Chim, 35, 161; also Scher, J, 5, 278. 

Ann. Chim. 64, 42; also N. Gehl. 5, 713. 
GoBEL. N. Tr. 10, 1, 26; also Br. Arch. 12, 74. 
Theod. Gruner. N. Tr. 2-1, 2, 55. 

Pelouzb. Ann. Chim. Phys. 50, 297; abstr. J. pr. Chem. 3, 54. 

q2 



84 AMTL:. 0XTG9N NVCLBQS C^'HW 

WEN1SEL0& Ann, Fharm, 15, 147- 

Ad. Eduard Arppe. De Acido pyrotariarico, Helsingforsiie, 1847. Sbort 

abstr. Ann, Fharm. 66, 73. — Further: Ann. Fharm. 87, 228; 

abstr. F^Mrm. CeiUr, lS5i, 106; «/. pr. Chem- 02, 54; Arch.ph.nat 

25, 184. 
ScBLiKPEif. Ann, Fhatm. 70, 131. 

BretuuftintUure, hrenxliehe, hretutige Weinsteintdnre, Acide pyroimiariqtte.'-^ 
Rfinirdrd as a peculiar acid by Guyton Monreau ; pronounced to be pyro-acetic acid 
by Pourcroy & Yanapelin ; again recognised as a peculiar acid by V. Rose, with whose 
opinion Pourcroy & Vanquelln afterwards agreed. 

Formation. 1. By the dry distillation of tartaric acid^ racemic acid, 
and cream of tartar. Perhaps in this manner; 

•cmK)'* - C>»HH)« + 6C0« + 4H0. 

Preparation. A. From Tartaric acid. — 1. The best method is to 
fill a retort three-foarths with a pnlverised mixture of equal parts of 
tartaric acid and pumice-stone (comp. z« 268), and raise the hc^at giudually 
so that the distillation may last 12 hours. The mass then swells up and 
yields a much larger quantity of pyrotartaric acid, so that the distillate 
crystallises when left at rest, and much less acetic acid and erapyreumatic 
oil than when no pumice-stone is used. The pale yellow distillate'is mixed 
with water; freed from the oil by means of a wet filter; evaporated till a 
crystalline film forms on the surface; set aside at 15°; the mother-liquor 
(which yields coloured crystals), allowed to drain from the resulting 
crystalline mass; this mass pressed between paper; and the aqueous solu- 
tion poured into nitric acid, then heated and set aside, whereupon it yields 
perfectly pure crystals. — The coloured crystals obtained from the mother- 
liquor may likewise be spread out on several sheets of bibulous paper; a 
number of small basins filled with absolute alcohol placed around them; 
and a bell jar having its inner surface moistened with absolute alcohol, 
inverted over the whole; the alcoholio solution of the oil, with only a 
trace of acid, then soaks into the paper, and a snow-white, but still 
odorous acid remains. By solution in water and heating with nitric acid, 
this acid is rendered inodoroas. By this process, 100 pts. of tartaric acid 
yield 7 to 8 pts. of pyrotartaric acid. (Arppe.) 

2. Tartaric acid or eream ef tartar (crude tartar yields nothing) is 
distilled alone in the dry state. From the watery distillate, which must 
be separated from the empyreuraatie oil, and contains acetic and pyrotar- 
taric acid (and pyroracemic acid, according to Berzelius), the pyrotartaric 
acid is either separated by repeated crystallisation and digestion with 
animal charcoal; — or the liquid is saturated with potash, and the pyro- 
tartrate of potash purified by repeated crystallisation, digestion with 
animal charcoal, filtration, and subsequent distillation with dilute 
sulphuric acid, whereupon the pyrotartaric acid passes over, partly with 
the water, partly sublimed in needles. (V. Rose.) — Pulverised cream of 
tartar (which must be heated above 400^) does not swell up, but yields a 
large quantity of carbonic and acetic acid, together with, first a thin 
yellow, then a viscid brown oil, and an acid liquid containing a small 
quantity of pyrotartaric acid. Tartaric acid, on the contrary, swells up 
into a viscid mass, and froths over (and, according to Weniselos, yields 
no pyrotartaric acid, but if continually stirred with a platinum wire, 
behaves like cream of tartar. (Arppe.) — If the tartaric acid be distilled 



PTROTARTARIC ACID» B8 

ftt a temperature below 190% the dietill&te jiMu^ (m evaporation^ eoloar- 
less crystals of pyrotartatic acid, which may be completely purified by 
means of charcoal; but if the distillation bo carried on between 200° and 
300% the distilhitei which is rich in orapyreumatic oil, must be evaporated 
to a syrup in a retort; then distilled to dryness with a fresh receiver; 
and the resulting distillate expend to a very lew temperature, or erapo* 
rated in vacuo, whereupon It Is resolvisd Into empyreumatio oil and 
yellow crystals, which must be pressed between paper, and purified by 
digestion with animal charcoal and crvstallisation. fPelonze.) — To 
render the thus purified, but still yellowish acid, perfectly white, Qbbel 
saturates it with carbonate of lime; evaporates the solution to dryness; 
extracts the empyreumatio oil from the residue by absolute aleohol; then 
dissolres it in boiling water; precipitates the lime by a proportional 
quantity of oxalic acid; then filters and evaporates. — Instead of car<* 
bonnte of lime and oxalic acid, carbonate of baryta and sulphuric acid 
may be used. (Gruner.) — The acid which remains in the mother-liquor, 
and is contaminated with a large quantity of empyreumatio oil, cannot 
be decolorised with charcoal, but the colour may be removed by heating 
and evaporating it with a small quantity of fuming nitric acid. (Weni- 
selos.) But this impure acid (not the pure acid) is decomposed by nitrio 
acid. (Arppe.) — If the coloured acid be distilled till the residue is 
black and nearly dry, the nearly odourless crystalline acid which passes 
over, pressed between paper and dissolved in water, the solation poured 
into nitric acid, heated, and left to crystallise, and the crystals melted^ 
the acid is obtained perfectly pure. 

B. From Sebacic acid. — 1 pt, of sebacic acid and 30 pts. of nitrio 
acid of sp. gr. 1 *4 are digested for 8 days in such a manner that the 
greater part of the acid may run back into the flask; fresh nitric acid 
atlded from time to time as long as red fumes continue to escape; the 
residue diluted with an equal quantity of wateri evaporated over tho 
water-bath in a basin to a syrup, with continual addition of water, as long 
as nitrio acid continues to escape: and the syrup sot aside over oil H 
vitriol to crystallise. (Schlicper.j 

Properties. Crystallises, either by sublimation or from water, in 
colourless four-sided needles (V. Rose); needles united in stars, and 
small laminm united in spherical masses (Gruner); transparent, colourless, 
rhombic prisms, with acuminated ends, united in stars and spherules (Arppe); 
oblique rhombic prisms, truncated at the acute lateral e<lges. (Weniselos.) 
Melts at 100** ^Gruner, Pelouzo, Arppe); at 107° to 110** (Weniselos); 
solidifies in a raaiated mass on cooling (Gruner); gives off white fumes a 
little above 100*^ (Gruner, Arppe); boils without decomposition at 140^ 
to 150** (Weniselos); at 188®, with partial decomposition (Pelouze); begins 
to bpil at 190% the boiling point then gradually rising to 220° (Arppe), 
and may be sublimed without residue (V. Rose), in dendrites and stars 
(Weniselos), in shining needles (Schiieper). When pure, it is perfectly 
colourless (Gruner, Arppe); tastes very sour (Rose); like tartario 
(Pelonxe); or suecinie acid (Schiieper). 

. Pelouxe. Arppe. Schiieper* 

CrywtaU dried in ifdeuo. a, b, a. c. 

10 60 .... 45-48 .... 45-86 .... 46-38 .... 45*55 .... 45-35 

8 H 8 .... 6-06 .... 6-ir .... 6-00 .... 6-01 .... 6-09 

8 O 64 .... 48-48 .... 47-97 .... 47-62 .... 48-44 .... 48-»6 

' C*»HW........ 132 ...: 100.00 .V. 10000 .... 100-00 .... 100-00 .... 100-00 



86 AMYL: OXtGEN NUCLEUS C»«H»02. 

a. is the add obtained from tartaric acid ; h. from racemic, and e. from sebacic 
acid ; the latter, solidified over oil of yitriol to a white, friable, somewhat glutinous 
mass, was analysed after fusion. 

100 pts. of crystallised acid give off 8 pts. water between 90^ and 100"*, retaining 
their crystalline form but becoming turbid ; 100 pts. of the crystallised acid mixed wiih 
300 pts. of lead-oxide and with water, and evaporated, give off 8 pts. water between 
90** and 100**, then 12-107 pts. more between 125° and 150^. (Gruner.) [No other 
chemist found the above 8 p. c. water of crystallisation.] 

Decompactions, 1. The acid, when carefallj heated in contact with 
the air, volatilises completely without decomposition (Schlieper); but 
when heated to the boiling point in a retort, it suffers partial decomposi- 
tion, and yields, toother with sublimed acid, a watery liquid containing 
acid, a yellow oil containing pyrotartaric acid, lighter than water, and 
Laving a sweet taste, (which however Weniselos denies,) and leaves in 
the retort a resin (Gruner), and ultimately charcoal (Weniselos). When 
pyrotartaric acid is kept for some time in a state of ebullition, whereupon 
it gives off vapours which excite coughing and smell somewhat like 
acetic acid, the residue crystallises but partially or not at all on cooling, 
and is found to be converted into oily anhydrous paratartaric acid 
(C^^H'O'^'), mixed with a certain quantity of unaltered pyrotartaric acid 
which gradually crystallises out. (Arppe.) — 2. The acid when heated 
strongly in contact with the air, turns brown, burns with a red-blue 
ilame, • and leaves a small Quantity of easily combustible charcoal. 
(Gruner.) — Chlorine gas passed for a few hours through aqueous pyro- 
tartaric acid, converts it, according to Gruner, into an acid exhibiting the 
reactions of citric acid; according to Weniselos, on the contrary, it exerts 
no action. — Hot strong nitric acid does not decompose pure pyrotartaric 
acid, 'but decomposes that which is contaminated with empyrenmatic 
oil, &c, (Arppe.) Gruner obtained with an acid which was )>erhaps not 
quite pure, a small quantity of hydrocyanic acid, and a substance which 
coloured the liquid yellow. Weniselos likewise observed that the distil- 
lation of the acid mixture was attended with partial decomposition. ~^ 
3. Hot oil of vitriol carbonises pyrotartaric acid (Gruner), and its solu- 
tion in dilute sulphuric acid likewise becomes coloured on boiling. 
(Arppe.) — 4. Pyrotartaric acid distilled with glacial phosphoric acid 
yields, first, pure anhydrous pyrotartaric acid, then also the hydrated 
acid; the residue however becoming carbonised. (Arppe.) — The acid is 
not decomposed by boiling with mercuric oxide or with nitmte of silver. 
(Gbbel.) 

Comhinations, Pyrotartaric acid dissolves in 4 pts. of water at 12*5° 
(Gbbel), in 3 pts. of water at 15° (Gruner), in \\ pt at 20° (Arppe). 
The solution does not decompose by keeping or by exposure to the sun 
(Weniselos), or by boiling (Arppe). 

It dissolves in cold oil of vitriol without blackening. (Schlieper.) 

Pt/Totartrat€B. — The acid forms neutral or bibasic salts = C^*H^M'0*,0', 
and acid or monobasic salts = C'°H'MO*,0*. It has a great affinity for 
bases. All its salts are crystallisable (Ar])pe); they sustain a heat of 
125° to 150° (most of them indeed of 200°, according to Arppe), but are 
decomposed between 250° and 300°. (Gruner.) In this decomposition 
the salts of the fixed alkalis give off water, then turn brown, froth up 
and give off gas, a yellow acid watery liquid, a thick stinking oil, and 
leave a carbonate of the alkali mixed with charcoal. The pyrotartrates 



PYROTARTARIC ACID. 87 

of the heavy nietals likewise yield an acid watery distillate and an oily 
distillate. (Graner.) The pyrotartrates^ when heated in contact with 
the air^ emit an offensive odour, and barn with a yellow smoky flame. 
(Graoer.) Heated with sulphnric acid^ they yield a snblimate of pyro- 
tartaric acid (V. Rose), and when heated with sulphuric acid and pero:s:id0 
of man^nese, they give off formic acid. (Gruner.) They are nearly all 
soluble in water, but dissolve very sparingly in alcohol, which rather 
precipitates them from their aqueous solution. (Arppe.) 

PjtrotartraU of Ammonia,^ a, Bibadc, C^°H«(NH*)*0«. —Formerly 
known only in the aqueous solution which, when evaporated, gives off ammonia and 
leaves the salt * (Arppe.) — •][ Obtained by passmg dry ammoniacal gas into 
a solution of pyrotartaric acid in alcohol of sp. gr. 0*80, whereupon the 
monobasic salt b first separates in delicate crystalline needles, and on 
continuing the passage of the gas, the crystalline mass re-dissolves almost 
entirely, and subsequently the neutral salt is deposited in the form of a 
white powder. — A better mode of preparation, however, is to pass the 
ammoniacal gas into the alcoholic solution of the acid, only till the acid 
salt is formed; then add alcohol saturated with ammonia, as long as a 
precipitate continues to form; then again pass the gas through till the 
solution becomes nearly transparent, and lastly saturate the liquid 
completely with ammoniacal gas after having poured it into another 
vessel. — • This mode of proceeding precludes the possibility of the neutral salt beixig 
contaminated by any portion of the add salt remaining undissolved. (Arppe.) 

White powder, consisting of short microscopic prisms; smells slightly of 
ammonia when heated only a few degrees; between 90^ and 100°, it gives 
off ammoniacal vapours, and is converted into the acid salt, which may 
be heated to 140° without further decomposition : 

C"H«(NH^)»09 - CWH7(NH<)0^ + NH». 

100 pts. of the neutral salt, heated to 115", yielded 90*19 pts. of the add salt ; and 
100 pts. heated to between 135** and 140^ yielded 88*94 pts. of the add salt. By 
calculation the quantity should be 89*76 p. c. [166:149 » 100:89*76.] Henoo it 
appears that a certain amount of decomposition takes place a little below 140**. — 
With potash, the salt gives off ammonia in considerable quantity. It 
dissolves very easily in water, sparingly in cold alcohol, and is decom-* 
posed by boiling alcohol, with evolution of ammonia and formation of 
the acid salt. (Arppe, Ann. Pkarm, 87, 229.) %. 

6. Monobasic. — Acute rhombohedrons, truncated even to the disap- 
pearance of the terminal edges. (Fig. 153.) Cleavage parallel to p. 
(Weniselos.) Small rhombic octohedrons and rhombic prisms, which 
assume a laminar appearance from shortening of their principal axis 
(Arppe); small four-sided needles. (Gruner.) The crystals are transpa- 
rent (Gruner, Arppe); strongly acid (Weniselos), permanent in the air« 
(Gruner, Weniselos.) They do not give off any thing at 100^, but begin 
to decompose at 140°. (Arppe, vid. sup.) — T The salt when heated in a 
distillatory apparatus, deliquesces to a viscid syrup at a temperature 
somewhat above 140°, ^ving off ammoniacal vapours; then assumes a 
darker colour and throws off bubbles : and at 150 , enters into a state of 
tranquil fusion. The residue then decomposes but slowly^ not boiling till 
it becomes heated to 160°; the boiling point remains constant for awhile 
at 176°; and rapid decomposition begins at 295°, a shining carbonaceous 
residue being left in the retort. The distillate consists at first of ammo^ 
niacal water, accompanied by a sabstance -which orystallisOf out 90 



aa AMYL: OXTOBN MUCLBU8 C'«H»0>« 

etl^poration; afterwards there paases over an alkaline, then an aoid oily 
liquid, which eolidifies at 0° or when eraporated; and lastly a neutral 
oil which solidifies in the liock of the retort The crystalline body which 
separates out during the entire operation is bipyrotatiramide C^^NH^O^ 
(Arppe.) 

C»«H7(NH^)0» - 4H0 « C^WO^. %. 

The crystals dissolve readily in water (Oruner), and with difficulty in 
boiling alcohol, Whence they tepto^te in the form of a etystaUine powder 
on cooling. (Arppe.) 



Cfry^ialt, 
IOC 60 


.... 40-27 
.... 9-39 
.... 7-39 
.... 42-95 


Arppe. 
.... 40-03 

.... 7-39 




N 14 

11 H i U 




8 O 64 








C^«H'(NH*)0» .... 149 


.... 100-00 







Pyrotartratt of Fota^, — a. Bihoiie^ — The aqueous acid exactly neu-* 
traliied with carbonate of potash, and eraporated to a syrup, solidifies in 
flat prisms, which, in dry air, or at 25® even in damp air, give off water, 
swell up, and are converted into nodules consisting of microscopic neediest 
These crystals give off their 2 At water at 200^; melt without decompo- 
ilition at a tehiperature somewhat above 200°; and at a higher tempe- 
fatttre, swell up and give off ettpyreumatic vapours. The dry salt, the 
nodules and the prisms all deliquesce in a cold damp atmosphere. The 
nodules, but not the anhydrous salt, dissolve in hot absolute alcohol, and 
the solution, deposits crystals on cooling; but from the saturated aqueous 
solution, alcohol precipitates the salt in oily drops. (Arppe.) 

a. Arppe. b» Gmner. 

2 KO 94-4 .... 41-69 .... 4200 2 KO .... 94-4 .... 38-63 .... 3782 

CWH«0« 114-0 .... 50-36 C1oh«0«. 1140 .... 46-64 

2Hb 18-0 .... 7-95 .... 7-81 4 HO .... 360 .... 14-73 .... 14*62 

C"H«K208+2Aq 226-4 .... lOO'OO +4Aq... 244*4 .... 100-00 .... 

a. at« the nodulai dried over oil of vitHol within a bell -jar oontatning air; h, was 
Qbiatiied by Omner ia iodistinct crystals, which were perhaps identical with Arppe's 
flat prisms. 

6. M<moba$ie. — Pint obserred by Fooreroy and Tanqnelini who conipared it 
with cream of tartar, whereas Pelotise denies the existence of an acid potash*sa1t. 
Precipitated from the saturated solntlon of the salt a by pyrotartaHc acid 
in the form of h crystalline powder. (Arppe.) One-half of a solution of 
pyrotartaric acid is exactly saturated with carbonate of potash, the other 
half then added, and the liquid evaporated. Large, transparent, oblique 
rhombic prisms. (Weniselos, Arppe.) They do not give off any thing 
at 200^ bdt when more strongly heated, they first give off acid, then swell 
np and evolve empyrenmatic products. They dissolve in water somewhat 
less readily than the salt a, and with difficulty in boiling alcohol, which 
takes away a portion of the acid, and on the other hand throws down^ 
eiystoli mm tkt nUnnM aqueons solntioiu (Arppe.) 



PTttOTAttTAUC acid; 8^ 

€hy$iai9i Wwisdog. Airppe. 

KO 47-2 .... g7*73 .... 26-56 27'67 

CWflW 123-0 .... 72-27 

C»H7K0« 170-2 .... 100-00 

PyroUxrtrate of Soda, — a, Bihatic. — The acid saturated with carbonate 
of soda yields by slow evaporation, large crystalllDe lamiuce with ragged 
edges, and^ by quick evaporation a syrup which solidifies in a crystalline 
mass on cooling. (Arppe.) Soft transparent needles united in spherules 
and permanent in the air. (Gruner.) The above-mentioned crystalline 
laminae give off nearly all their water on exposure to the air and crumble 
to a white dust; give off all their water at 200^; and decompose at a 
stronger heat without fusion or intumescence. They dissolve readily in 
water, but not in alcohol, even at the boiling heat; alcohol indeed renders 
the aqueous solution turbid. (Arppe.) 

Needlet, Graser. Todies, Arppe. 

2NaO 62-4.... 27-08 .... 27-2 2 NaO .... 62-4.... 21-94 .... 21-84 

CMH«0« 1140 .... 49-48 C«H«0« .... 1140 .... 4009 

6 HO 64-0 .... 23-44 .... 20-9 12 HO .... 108-0 .... 37-97 .... 37-90 

.11 1 1 I I III I . ■ 

C»H«Na*0«+ 6Aq 230-4 .... 100-00 -f- 12Aq.... 284-4 .... 100-00 

h. Monobasic. — When the solution is evaporate oyer oil of vitriol 
within a bell-jar, there remains a dense crystalline mass consisting of 
microscopic rhombic prisms, which, after drying in the air, give off 
nothing at 200'', and contain 20-30 p. c. soda; therefore ss C^^H^NaO^ 
(Arppe.) The mlt dissolves readily in water, (Weniselos.) 

A mixture of equal nmnbers of atoms of the bibasic potash and soda-salts ieaves a 
gam when evaporated. (Arppe.) 

Fyrotartraie of Baryta, — a, Bihasic, — When the warm aqueous acid 
IS completely neural ized either by baryta-water or by carbonate of baryta, 
and the solution eraporated, the bibasic salt is deposited in the form of a 
white, shining, crystalline powder, which, when examined by the micro- 
scope, is fotlnd to consist of obliqne rhombic needles. This crystalline 
powder begins to give off its water of crystallisation at 90°, parts with 
half of it at 100°, the whole at 160°, and undergoes no further decom« 
position at 200°. The crystalline powder dissolves readily in water either, 
hot or cold, and is precipitated therefrom by alcohol. (Arppa) Heuce 
the clear aqueous mixture of chloride of barium and pyrotartaric acid or 
a soluble pyrotartrate, gives a precipitate in a few hours after the addition 
of alcohol and atnmonia. (Arppe.) 

CryttdUine powder. Arppe. Gmner. 

2.BaO 153-2 .... 50-53 .... 50-61 .... 49*70 

C»H«0* 114-0 .... 37-60 

4 HO M 36-0 .... 11-87 .... 12-00 .... 12-02 



■*■ 



C^WBa«0» + 4Aq .... 303*2 .... 10000 

5. Monchatie, — One-half of a portion of the aqueous acid is satomted 
with cturbdnate of baryta, then mixed with the other half and erapo* 
mtad. It ihett ePoreflOei And yields needlw united in globoJar radiate^ 



90 AMYL : OXYGEN MUCLBUS C>«H«0». 

masdes. These crystals soon become dall on exposare to the air^ give off 
half their water at 90% and the whole at 150% leaving 92*74 p. c. of 
anhydrous salt, which at a stronger heat is converted into 61 -^8 p. o. 
of bibasic salt, and at a red heat, leaves 84*86 p. c. of carbonate of 
baryta. . The needles give up half their acid to alcohol. Thev dissolve 
very readily in water. (Arppe.) — Weniselos obtained the salt in stars 
which were permanent in the air and reddened litmus. 

KeedUi, Arppe. 

BaO 76-6 .... 35-20 34*86 

C^H^Of 123-0 .... 56-53 

2 HO 18-0 .... 8*27 7*26 

CWH^BaO'' + 2Aq .... 217*6 .... 100*00 

Arppe once obtained from an indefinite mixture of the acid and barjta-water, 
besides the above-mentioned needles, four and six-sided prisms which exhibited the 
same reactions as the needles, but contained 40*83 p. c. baryta. 

Pyrotariraie qf baryta andpotath, and PyrotartraU of baryta and wda, nhose 
existence is maintained by Gruner, cannot really be obtained. (Arppe.) 

Pyi'olartrate of Sirontia, — a. BUxuic. — The aoncons acid, neutralized 
by continued boiling with carbonate of strontia, yields after evaporation, 
small prisms easily soluble in water, and precipitated therefrom by 
alcohol. (Arppe.) Four-sided prisms sparingly soluble in water^ inso- 
luble in alcohol. (Gmner.) 

Prums air-dried. Arppe. Gmner* 

2 SrO 104 .... 44*07 .... 43*07 .... 40*13 

CWH«0« 114 .... 48*30 

2 HO 18 .... 7-63 13-88 

C:ioH«Sr»0" + 2Aq 236 .... 100*00 

Grnner^ according to his analysis, assigns to the salt 4 At water. 

b, JHonobadc. — By digesting the dilute acid with carbonate of strontia 
and evaporating the filtrate, soft nacreous, microscopic lamime are 
obtained which part with all their water at 130°, give off acid vapours 
at 135°, yield half their acid to alcohol^ and are soluble in water. 
(Arppe.) 



jMinin€t, 

SrO 52 .... 26-94 

CWH'O? 123 .... 63*73 

2 HO 18 .... 9-33 


Arppe. 
...« 26-43 

.... 9*39 






C»0H7SrO8 + 2Aq 193 .... 10000 





Pyrotartrate of Lime, — a. Bibasic. — Precipitated on mixing the concen- 
trated solutions of chloride of calcium and bibasic pyrotartrate of potash. 
By boiling the aqneons acid with carbonate of lime, till it is neutralized, 
evaporating the filtrate, and cooling, the salt is obtained in the form of 
a white crystalline powder, which, when examined by the microscope, is 
teen to consist of four-sided prisms. The salt gives off its water at 160^ 
but in other respects remains unaltered at 200^ It requires nearly 100 
pt& of boiling water to dissolve it} dissolves readily ip bydrocblorici 



PTROTARTARIC ACID. 91 

nitric or acetic acid; bat is insolable in alcohol. (Aippe.) The aaueons 
solution of the acid salt gives off part of its acid when evaporatea^ and 
deposits the bibasic salt in soft shining needles united in spherical masses^ 
which give off their water when exposed to the air^ and dissolve sparingly 
in water. (Ghrnner.) 

CryttaU, Arppe. 

2CaO 56 .... 27-19 .... 2M2 

CWH«0« 114 .... 55-34 

4 HO 36 .... 17 47 .... 17-23 

C^^H^CaW + 4Aq .... 206 .... 100-00 

b. With S At Acid, — The salt a dissolves readily in aqueoas pyro- 
tartaric acid^ and the solution, when gently evaporated, yields crystals 
which give off their water at 110^, the acid then also beginning to evapo- 
rate. (Arppe.) The mono-acid salt cannot be obtained ; for, on nentralising 1 pt. 
of the aqueoas acid with lime and adding another 1 pt., a large quantity of bibasic salt 
is precipitated, and the remaining very add liquid deposits on evaporation an additional 
quantity of bibasic salt, so that ultimately nothing but the pure add is left. (Arppe.) 





CrytiaU. 




Arpp«. 


CaO 


#at*t •••••■• ■••••••••••••••■ 


. 28 


6-47 .... 6-36 


C»H707 




. 123 


.... 28-40 


2 CWH808 




. 264 


.... 60-97 


2 HO 




. 18 


4-16 . . 4'77 









CWH'CaO* + 2CWH80» + 2Aq.... 433 .... 10000 



Pyrotartrate of Magnesia. — a. Morvobadc. — a, ifo^^Ttetia o^ dissolves 
very readily in the aqueous acid, forming a perfectly neutral liquid, 
which, when evaporateid over oil of vitriol within a bell-jar containing 
air, leaves, first a viscid gum, then, after evaporation, an easily friable 
mass. This mass gives off water at 90°, but even at ITO"*, at which 
temperature further decomposition begins, it gives off only 24*41 p. c. 
in all. — p. When the above solution is evaporated merely to a syrup, 
and a small quantity of water added by drops, the syrup yields crystals, 
and is converted in a few hours into a dry crystalline mass, which, under 
the microscope, appears to consist of six-sided laminar prisms; it gives off 
nearly all its water at 130^ and the small remaining quantity at 200% 
in all 40*57 p. c. — The salts a and /8 dissolve very readily in water, 
but are insoluble in alcohol which precipitates them from water; the 
aqueous solution of the salt /3 again yields crystals when evaporated; but 
that of the salt a leaves a syrup which does not crystallise till water is 
dropt into it. (Arppe.) 

a. Dry gum. Arppe. 

2MgO 40 ... 19'23 18-48 

C»^HH)« 114 .... 54-81 

6 HO 54 .... 25-96 24*41 

C»H«Mg»0» + 6Aq 208 .... 10000 

j3. Crystalline ma9$, Arppe. 

2MgO 40 .... 15-27 15*95 

C'^'H 0» 114 .... 43*51 

12 HO 108 .... 41-22 40*57 

CioH*Mg>0» -f 12Aq .... 262 ..., 10000 " 



\H AMTL I OXYgSN KUCLBUk O^WO^. 

k Ifanoboii^, — Gummy. (Alrpp^) 

P^n>tnrtrtite of Olucifia, — Thd aqueous Aoid sttturated witli hydrate 
Xt glttcina^ leaves, when eraporated over oil of vitriol withia a receiver 
containing air, the acid salt h, in the form of a mass which is viscid 
at first but afterwards becomes cryBtalline. This acid salt melts at 110^, 
gives off acid Vapours^ and at 180° leaves the neutral salt a> (Arppe.) 

a, Arppe. b, Arppe. 

2 GO 25-4 .... 18-22 .... 17'93 GO 12-7 .... 4-71 .... 470 

QioHSO* 1140 .... 81-78 CWRW 1230 .... 45-98 

CWH*0» 1320 .... 49-31 

C'«H«G*0» 139-4 .... 100-00 CWH'Ga»,C»»H«0« 267-7 .... 10000 

Pyfntatinxte 9/ Alumina. — a. Mwiobano. — 1. By boiling still moist 
hydrate of alumina with a quantity of aqueous acid less than suiiieioni 
to dissolve it^ the salt is obtained in the form of a heavy powder 
insoluble in water. — 2. Precipitated in considerable quantity on mixing 
hydrochlorate of alumina with bibasic pyrotartrate of soda^ m an excess 
ot which. it dissolves. (Arppe.) 

Arppe. 
(1.) (2.} 

A1»0» 51-4 .... 28-03 27'26 .... 27-30 

C>oil»0« 1140 .... 62-16 

2 HO 180 .... 9-81 7-13 .... 6-93 

183-4 10000 

5. Acid. — Hydrate of alumina, while still moifit^ dissolves slowly in 
the aoueous acid, and yields by evaporation, crystals, from which, when 
heated with water, 2 per cent, of hydrate of alumina separates. (Arppe.) 

Green Chromic Hydrate disaolves sparingly in the boiling aqueous arid, and the 
green stronglj acid solution yields hy evaporation, green-spotted crystals of the acid ; 
blue chromic hydrate forms with the cold aqueous acid, a blue solution, which becomes 
perfectly deoolorided by evaporation to dryness. (Arppe.) 

Uranie Pyrotartrate, — Bibasic pyrotartrate of potash added to uranic 
nitrate gradually throws down a white crystalline powder. (V. Rose.) 
The aqueous a<iid dissolves uranio hydrate so abundantly, that it 
loses its Sour taste; and the yellow solution, when evaporated and 
cooled, deposits a yellow powder which becomes yellowish white when 
dry, dissolves readily in water, forming a yellow solution, and is preci- 
pitated therefrom in large quantity by alcohol in yellow flakes. Its 
aqueous solution, evaporated with a larger quantity of acid, leaves a 
crystalline mass. (Arppe.) 

Precipitated hy alcohol, 

4 U*0» 576 

C»«H«0« 1 14 

2 V^Wai 246 

4 HO 86 





Arppe. 


.... 59-26 .... 59-45 


.... 11-73 




.... 25-31 




.... 3-70 .. 


5-41 



CMH«(2UaO*)0»,2[C«>Hr(U«0«)0»] + 4Aq .... 972 .... 10000 

[As Arppe did not find the lots of weight to amovnt to 5*41 p. e. till he heated the 
salt to 200^ it is possible that aei4 Hay hare passed off With the water.] 



PYROTASTABIC APPt 0? 

Pjfrotarirai4 of Manganese. — Curbqnate of miuaffiMiese 4iMolve« slowly 
in the cold aqueous acid, quickly in the aame when ()ot, forming a not 
perfectly neutral liquid, which leaves a gum when evaporated. This 
gum still retains 2 At.. water at 200^| and decomposes at a stronger heat 
before the water escapes. It dissolves readily in water, and is precipi- 
tated tlierefrom hy alcohol, as a curdy massi which difTqsos itself in a 
lavger quantity of alcohol, in the form of a reddish, heavy, granular 
powder. (Arppe.) 

At 200". Arppe. Arppe. 

« MnO n .... M*30 .... 34-90 2 MnO .... 12 .... SO .... 29*80 

C'»H«0« lU .... 65-88 C'»H«0» 132 .... 5$ 

2 HO , 18..,. 8-82 4 HO 36 .... 15 .... 14'6l 



■^- 



C»°H«Mn«0> + 2Aq.... 204 .... 100-00 + 6Aq .... 240 .... 100 

Antlmonic oxide is quite Ipiglable in the aqueous acid (Arppe}i or dissolves very 
sparingly. (Gruner.) 

PyrotariraU of SitmuiK-^^Ihe heated acid does not dissolve the oxide 
or the carbonate of bismuth, and but sparindy the recently precipitated 
hydrate. The solution saturated as completely as possible, becomes 
turbid when boiled and clenr again on cooling. When evaporated, it 
leaves the crystallised acid ^nd a gummy substance. With water it forms 
a precipitate, which increases when the liquid is heated, and diminishes 
on further addition of water. Tbo same precipitate is formed by alcohol. 
The precipitate ignited in a glass tube, leaves a residue which, if exposed 
to the air while yet warm, takes fire and burns away, leaving oxide of 
bismuth. (Arppe.) 

Arppe, 
Air^dried pp€9ipiM9» o* 3« 

4 BrO» 948 .... 71»49 .,.. n»64 .... TMS 

3 C»<>H«0« 342 .... 25-79 

4 no 3 6 .... 2-72 .... 2'66 .... 2-78 

CWH8(2Bi20*)08,2tC«»H7(Bi20*)08] + 2Aq.... 1326 .... 10000 
a was obtained witli water ; b, with alcohol. 

Pyrotartraie of Ztn^.-t^, Polyhade. — When the somewhat acid solu^ 
tton of h is evappn^ted to 9> soft gun; 4pd redissolved in water, there 
remains a small quantity of powder containing 55 per cent of zino 
oxide. (Arppe.) 

h, BUxmc, a, Anhydrous, — - The metal dissolves slowly in the ^id, 
the oxide quiclvly at a boiling heat. The syrup obtained by evaporating 
the acid filtrate, forms with alcohol a curdy coagulum, which soon changes 
to a granular powder and dissolves in water, leaving a small quantity of 
the salt a. But by preoipitatiMff a very acid solution with atoQnol, a f ery 
soft powder is obtainedi which dissolves completely in oold water, forming 
a solution whiq);i becomes turbid when boiled. Vid. analysis h q> 

p, JBydraUd, — Carbonate of zino disolves very rapidly in the hot 
acid; and tbo pearly neutral solution leaves on evaporation, a thiek syrqp 
which gradually forma granules, and on addition of a small quantity of 
water, is oomplet^ly converted into a mass which is soluble in water, and 



94 AIIYL: OXYGEN NUCLEUS C^BW. 

must be pressed between paper; at 200^^ it gires off 14*90 p. c« or 4 At. 
water, retaining 2 At. (Arppe.) 

b, a. AtT'dried, Arppe. b, /3. Air-dried, Arppe. 

2 ZnO 80'4 .... 41'36 .... 41-53 2 ZnO 80-4 .... 32*37 .... 32*73 

C^HW 114-0 .... 58-64 C»H«0« 132-0 .... 6314 

4 HO 36-0 .... 14-49 .... 14*99 

C"'H«Zii?0« 194-4 .... 10000 + 6Aq 248-4 .... lOO'OO 

PyrotaHrale of Cadmium. — a. Bibanc, — a. With 4 At. water. — 
From the acid satarated with carbonate of cadmium, alcohol throws 
down a salt, which, after drying in the air, gives off 2 At. water at 100^, 
and the other two near the point at which it decomposes. (Arppe.) 

6. With 6 At water, — The acid satarated with oxide, hjdrated 
oxide, or carbonate of cadmium and evaporated to a thick syrup, 
gradually yields granules, and then, after being covered with a little 
water, and left to evaporate in dry air, solidifies almost entirely to a 
powder, which is freed from the acid mother-liquor by pressure between 
paper. It is quite neutral, gives off 12*73 p. c. (4 At.) water ut 200^ 
near its decomposing point, retaining therefore 2 At. It dissolves 
readily in water, and is precipitated from the solution by alcohol. 
(Ar})pe.) — The acid solution yields small four-sided prisms, which 
dissolve readily in water, contain 48*48 p. c. cadmic oxide after drying 
at 130°, and 32 p. c. after drying at 100 . Alcohol abstracts acid from 
them, so that neutral salt remains. (Gruner.) 

a, a. AtT'dried, Arppe. a, p. Air-dried, Arppe. 

2 CdO 128 .... 46*04 .... 45*91 2 CdO 128 .... 43*24 .... 43*13 

C»HH)« 114 .... 41*01 CMH«0«... 132 .... 44*60 

4 HO 36 .... 12-95 .... 12*67 4 HO 36 .... 12*16 .... 12*67 

CMH«Cd»0» + 4Aq 278 .... 10000 + 6Aq 296 .... 100*00 

5. Monobasic, — The solution of the salt a, mixed with as much acid 
as it already contains, leaves on evaporation, a viscid mass in which a 
few long slender needles gradually form. (Arppe.) 

• 

Stannous Fyrotartrate, — The acid does not dissolve metallic tin, but 
dissolves the protoxide and its hydrate with facility. The solution 
filtered from a yellow basic salt, becomes very turbid when mixed with 
water, and forms with alcohol a copious precipitate, which, after 
drying at 200^ contains 70*16 p. c. stannous oxide, and is therefore 
2SnO,C^^H%n'0^j it is decomposed by boiling water, with solution of only 
a very small portion. (Arppe.) 

Fyrotarti'ote of Lead, — a, Sexhasic,^-4}hiBAned by treating the salt b 
with ammonia and washing with water, which does not dissolve any of 
the lead. (Arppe.) ^ 

b, Quadrihasie, — The free acid or the bibasic potash-salt forms with 
basic acetate of lead a white curdy precipitate, soluble in acids and in 
excess of snbacetate of lead, but insoluble in water. (Pelouze.) The 
curdy precipitate obtained with the ammonia-salt^ and soluble in pyro- 



PYROTIRTASXC ACID* 95 

tart.irio aci<t^ cakes together in a few hours on the bottom of the vessel^ 
forming a hard^ yellowish white^ friable crust. (Schiieper.) 

Salt a. at 200<». Arppe. 

6 PbO 672 .... 85-50 8540 

C»H«0« 114 .... 14-50 

4 PbO,CWH«Pb«08 ^. 786 .... lOO'OO 

Salt h, at 100^ Arppe. 

4 PbO ., 448 .... 79*71 79*66 

CMH«0« 114 .... 20-29 

2 PbO,CWH«Pb»08 562 .... 10000 

Schlieper's salt described under b contains at 100** only 72*97 p. c. of oxide of 
lead. Bj treating the salt c with ammonia, Gruner obtained a whits powder, which 
contained at 130**, 76*55 p. c. lead-oxide and 3*09 p. c, water, and is therefore 
2PbO,C«>H«Pb»08 + 2Aq. 

€. Bibasic, — The free acid does not precipitate nitrate or neutral 
acetate of lead (Pelouze); it precipitates neutral acetate of lead after a 
while in bundles of needles (Fourcroy & Vanquelin, Weniselos); basic 
acetate of lead precipitates the same salt. (Arppe.) The bibasic potash- 
salt forms with neutral acetate of lead in a few hours^ crystalline nodules 
(V. Rose)^ white flakes, containing 66*05 p. c. oxide (Pelouze); if alcohol 
be added, the precipitation takes place immediately, — ^and with nitrate of 
lead, after a while, needles. (Weniselos.) By boiling the acid with lead- 
oxide, filtering from a basic salt, and evaporating and cooling, the salt 
is likewise obtained in needles, which however, according to Arppe (not, 
according to Gruner) are anhydrous. The needles lose their transparency 
on exposure to the air. (Gruner.) 'The salt melts on heating the liquid 
from which it has been precipitated, and forms oily drops. (Schiieper.) 
It yields by dry distillation, empyreumatic oil and a watery liquid con- 
taining acetic acid, and, when heated in contact with the air, gives off 
acid vapours, takes fire and then burns away with a glimmering light, 
even after the fire has been removed. (Gruner.) It dissolves very, 
sparingly in cold water (Weniselos), more readily in not water, from which 
it crystallises out on cooling; the solution of the precipitate in excess of 
nitrate of lead also yields four-sided needles. (Arppe.) 

Air-dried crystaU Gmner. Arppe. 

2 PbO 224 .... 59*89 59*02 .... 59*73 

C»H«0« 114 .... 30*48 

4 HO 36 .... 9*63 9*58 .... 9*65 

fn--| - - 111 - -- — ■ . . , J- 

CMH«Pb«08 + 4Aq.... 374 .... 10000 

Ferrous Pprotarirate. — The acid, especially when hot, dissolves iron 
with evolution of hydrogen. The solution reddens quickly, and forms 
red flakes with. water or alcohol. (Arppe.) 

Ferric Pyrotartrate. — a. With 18 At, Base, — Obtained by treating 
either of the following salts with excess of ammonia and washing. Has 
the appearance of hydrated ferric oxide. After drying at 100% it gives off 
1 0-48 p. c. water at 200. (Arppe.) 



96 AMYL:^ OXTQW NVCUIU8 C^HW- 

b, Sexbaiif* -^ Ferrjo bydrooblontie aatarirted witb '^mnloiiia aa far 
as possible witboat pennanent preoipitiitioii} fomis witb bib»aio pyrotarr 
trate of eoda^ a copious precipitate, which, after washing and drying at 
lOO"", appears hard and friable, gives off 8*49 p. c. water at 200 , is 
insoluble in water, very sparingly in acetic acid, but dissolves abundantly 
in nitric acid. (A rppe.) 



Salt n, drUd at \W. 

18 Fe^O* 1440 .... 8392 .. 

CWH«0« 114 .... 6-64 

18 HO 162 .... 1|'44 „ 


Arppa. 
82-94 

10-48 






1716 10000 

Salt k. dried at 100*. 

6Pe209 480 .... 74-08 

CWHW 114 .... 17-59 

6 HO 54 .... 8-33 


Arppe. 
.. 74-27 

8-49 







648 100*00 

In the salt a, Arppe assumes 20 Aq, which certainly agrees better with the 

analysis. 

c. With t At, £aie.mr^VeniQ hydroohlorate mixed with ammonia till 
a reddish colour just begins to appear, forms with bibasic pyrotartrate of 
soda, a red precipitate which has a gummy consiatence only when warm. 
This precipitate washed, first with water containing sal-ammoniao, then 
with pure water, and afterwards dried, appears brown, gives off 7*86 
p. c. water at 200^ and, when moistened with water, assumes a yellowish 
brown colour^ does not become gummy, and aearoely colonrs the water. 
(Arppe.) 

Dried at 100*. Arppe. 

4 Pe«0« 320 .... 44'69 44-64 

3CWHW 342 .... 47-77 

6 HO 54 ..,. 7-64 7*80 






716 MM 100-00 

d. Monobasic, — 1, SesquichloriJe of iron free from excess of aoidj 
is precipitated by the bibasic soda-salt; the red, very gummy precipitate 
collected on a filter after addition of sal-ammoniac, without which the 
liquid will not filter well; and washed by decantation after drying, 
because, if water were immediately poured upon it, it would become 
pitchy and stop up the filter. It is brown in the dry state, but red and 
gummy when moist. It dissolves sparingly in cold water (in 200 pts. 
according to Pelouze), formiug a clear liquid, which, in a few days, soli- 
difies to a stiff mnss. (Arppe.) 2. The solution of recently precipitated 
ferric hydrate in the boiling acid, if exhausted with alcohol, after evapo- 
ration to dryness, leaves a red, gummy residue of the same salt which 
turns brown after drying. 

Air 'dried, Arppe (1). Arppe (2), 

Pe?0« 80 ,... 83*47 33*01 .... 3V51 

C^ofl^O* 132 .... 66*23 

8 HO if .... 11*30 12-05 .... 11«07 



■^r-^-T^W"^^ ." ., -.. . 'W^^"'^'^~~"T~"»"*"""»1F*B^P" 



S39 IQO'OO 

Jht 12*65 and 11*07 p« c. water escape at 100*|b«t na inere* (Arppe.) 



PYROTARTAWC ACID. 97 

e. With 9 At. acid.-^ The eoneenir&ted acid disaolyes recently preci- 
pitated ferric hydrate pretty easily (not the dry), forming a reddish 
yellow^ very acid liquid which soon changes completely to a yellow crys- 
talline mass. This mass melts at 105°, giving off 1*81 p. c. water, and 
after evolving acid vapours, ultimately leaves 6*02 p. c. ferric oxide. It 
is therefore perhaps Fe»0»,9C*<»H«0«, 18 Aq., and the loss at 105** amounts 
to 3 Aq. On exhausting the crystalline mass with absolute alcohol^ 
there remains a brick-red powder, which is likewi.se insoluble in water, 
contains 31-99 p. o. ferric oxide at 200°, and is therefore 2Fe»0»,3C*^HH)». 
( Arppe.) By evaporating and cooling the brown solution of the hydrated 
oxide in the acid, Gruner obtained brown transparent needles, permanent 
in the air. 

Pyrotarirate of Cobalt. — a. Bessie. — By exhausting the salt 5 with 
alcohol and washing the residue with water. Rose-coloured salt, which 
when heated gives off water, to the amount of 17*27 p. c, at 200°, and 
turns blue; it contains 63*25 p. c. water. (Arppe.) 

5. Acid. — Hydrated protoxide of cobalt dissolves sparingly in the 
acid, forming a strongly acid liquid, which on evaporation deposits 
colourless crystals of the acid mixed with a sparingly soluble red salt. 
On neutralizing with ammonia, there is obtained a rose-coloured crystal- 
line powder containing ammonia, and dissolving with decomposition in 
water. (Arppe.) 

Pyrotctrtrate of Nickel. — a, Bilasic. — The hydrate dissolves very 
easily in the acid. On evaporating the green solution to a crystalline 
mass, and exhausting the residue completely with alcohol, there remains 
a green crystalline powder very sparingly soluble in water. This powder, 
after drying in the air, gives off 1 1 '62 p. c. water at 200°, and a little 
above that temperature, it slowly parts with the remainder, amounting 
in all to 15*89 p.c. without further decomposition. (Arppe.) 

Air •dried, Arppe. 

9NiO 75 .... 33-33 33*50 

Ci»H«0* 114 .... 60-67 

4 HO 86 .... 16-00 15*89 

C»H«Ni30« + 4Aq 225 .... 10000 

h, Biracid, — The solution of the hydrated oxide in the acid leaves, 
when evaporated under a bell-jar with oil of vitriol, first a syrup, then a 
crystalline mass, which melts at 115° and gives off 2*85 p. c. water, but 
emits acid vapours even at 1 20; in the free state, but not when dissolved 
in water^ it is decomposed by alcohol and yields the salt a. (Arppe.) 

CrystalUm ma$g. Arppe. 

NiO 37-5 .... 12-08 11-90 

a C"H*0« 228-0 .... 73-43 

6 HO 45-0 .... 14-49 

C»»H7NiO8,C'0H»O» + 2Aq 310-5 .... 10000 

Cupric Pyrotartrate. — a, Quadribasic. ^^When the asnre-colonred 
solution of the salt b in ammonia is evaporated with addition of water, it- 
becomes nearly decolorized and deposits greenish flakes, which after 

VOL, XI. H 



98 AMYL: OXYOBN-NUCLBUS C»»H*0«. 

drying in the air contain 51*40 p. c caprio oxide and are therefore 
4CuO,C»°HW, 4Aq. (Arppe.) 

6. Bibasic. — 1. The warm acid forma with cuprio oxide, a pale green 
salt, part of which remains dissolved in the excess of acid, forming a green 
solution, which, when evaporated, deposits green crystab of the salt 
together with crystals of the acid. (Grnner). — 2. The bibasic soda- 
salt, but not the free acid, precipitates cuprio salts bluish green. 
(V. Rose, Arppe), blue (Gobel), bluish (Weniselos). — The air-dried salt 
gives off its water at 130^ and at a higher temperature emits vapours 
having a strong odour of butyric acid. ^ Arppe.) The salt subjected to 
dry distillation appears to yield formic acid. (Grnner.) It dissolves in 
abiout 230 pts. of water (Pelouze), easily in acids and ammonia^ scarcely 
in alcohol (Arppe.) 

Xhied at 100\ GObel (2). 

2CuO 80 .... 37-73 37-76 

10 C 60 .... 28-30 28-40 

8 H 8 .... 3-78 2-84 

8 O 64 .... 30-19 3100 

Ci«H«Cu«08 + 2Aq 212 .... 100-00 lOO'OO 

Air^dried, Graner (1). Arppe (2). 

2CuO 80 .... 34-77 .... 34-18 .... 3457 

a*WO^ 114 .... 49-58 

4 HO 36 .... 15-65 .... 15-40 .... 1560 

C"H«Cu«08 + 4Aq 230 .... 10000 

The blue solntion of the salt b in ammonia leaves, when evaporated 
under a bell-jar, first a thick symp, then a dry mass, which contains 
86-41 p. c. of the dry salt b, and is therefore C*^H«Ca»0«,NHH). (Arppe.) 

Mercurous Pyrotartraie. -—The bibasic potash-salt, (not the free add, 
according to Pelouze), forms an abundant precipitate with mercurous 
nitrate. (V. Rose.) The dried white pulverulent salt contains 74*81 p. c 
mercurous oxide. In the moist state, it turns grey when exposedjto the 
sun. When heated, it sublimes partly undecomposed and leaves charcoal. 
(Harff.) It is nearly insoluble in water, easily soluble in nitric acid, 
somewhat in aqueous bibasic pyrotartrate of soda (Arppe), insoluble in 
alohol and ether. (Harff, N. Br. Arch. 5, 274.) 

The salt when suspended in water, is converted by ammonia, into a 
velvet-black, tasteless powder containing ammonia and 86*8 p. c. mer- 
curous oxide. (Harff.) 

Mercuric Pyrotartrate. — 1. The solution obtained by digesting 
mercuric oxide with the acid, yields on evaporation, a transparent, non- 
crystalline mass, from which cold water throws down a white powder. 
This powder redissolves when heated, and yields crystalline nodules on 
cooling. (Grnner.) The hot-filtered solution of mercuric oxide in the 
concentrated acid deposits a white powder on cooling. (Harff.) The 
solution of mercuric oxide in the boiling acid, when evaporated by heat, 
becomes turbid on cooling, and forms with water a precipitate which 
disappears on heating the liquid; the solution evaporated under a bell-jar 
leaves a mass consisting of very small globules or grains. (Arppe.) 



PYROTARTARIC ACID. 99 

2. The potash-salt (not the free acid^ according to V. Rose) added to a 
solution of mercuric nitrate^ throws down a white crystalline powder, 
having a metallic taste, and containing 60*18 p. c. mercuric oxide. This 
powder is decomposed by dry distillation, leaving a residue of charcoal; 
dissolves in 119 pts. of water, forming a solution which deposits a basic 
salt on boiling; it dissolves more readily in acidulated water, and in oil 
of vitriol, especially when warm; but is nearly insoluble in alcohol and 
ether. (Harff, N. Br, Arch,, 5, 276.) Corrosive sublimate forms with 
the sod«i-salt a scanty precipitate agreeing iu composition with that 
obtained by (1). (Arppe.) Corrosive sublimate forms with the acid, a 
white precipitate which disappears on agitation; then, after 12 hours 
a brown red precipitate; with the potash-salt, it gradually forms a white 
cloud, and then sdFter 1 2 hours, a brown precipitate. (Gobel.) 

The salt suspended in water is converted by ammonia into a white 
powder, which has a faint metallic taste, contains 77*9 p. c. merourio 
oxide and gives off ammonia when treated with potash. (HarfP.) 

Pyrotarlrate of Silver. — Bibasic pyrotartrate of potash (ammonia, 
according to Schlieper; soda, according to Arppe) precipitates nitrate of 
silver immediately and abundantly. (V. Rose.) The white precipitate 
resembles flakes of hydrate of alumina, and slowly dries up to hard trans- 
lucent lumps which yield a brown-white powder. (Schlieper.) Under 
the microscope, it is seen to consist of delicate needles; in the moist state 
it turns grey on exposure to light (poppy-blue according to Gbbel), gives 
ofi*, when strongly heated, vapours smelling of butyric acid, and dissolves 
sparingly in cold water, readily in nitric acid, acetic acid, and ammonia. 
(Arppe.) — The free acid forms with nitrate of silver, after 12 hours, a 
grey precipitato (Fourcroy and Vauquelin), and with acetate of silver, 
after 12 hours, a black-brown precipitate. (Gdbel.) 



10 c 

6 H 


JDried at 100». 
.,„ 6 .... 


17-34 .. 

1-74 .. 

62*43 .. 

18*49 .. 


Schlieper. Arppe. 

18*61 .... 17-36 

2-01 .... 1*88 


2Ag .. 

8 O 


216 .... 

,.,. 64 .... 


60*27 .... 62-29 

19*11 .... 18-47 









C»H«A«»08 346 .... 100-00 100*00 .... 100-00 

The soda-salt forms with bichloride of platinum, a scanty red-brown 
precipitate, which quickly changes to metallic platinum. (Arppe.) 

Pyrotartario acid dissolves readily in alcohol and ether. (Arppe.^ 

The empyreumatic oil which passes over in the dry distillation of 
tartaric acid, contains an acid different from pyrotartario acid, which crys- 
tallises in three or four-sided needles, precipitates hydrochlorate and 
sulphate of lime after a while in the crystalline form, and forms copious 
precipitates with neutral acetate of lead and mcrcurous and mercuric 
nitrates (not with nitrate of silver). (V. Rose.^ 

Gruner likewise observed a peculiar acid which crystallised like 
benzoic acid, volatilised readily in pungent vapours, but boiled when 
quickly heated, turning brown and leaving a large quantity of charcoal* 



H S 



100 AMYL: OXYGBN^KUCLEUS CWH«0». 



Conjugated Compounds of the Oxygen-nvdem C^^H^O*. 

Pyrotartrate of Methyl. 

C"HiH)« = 2C»H»0,C"H»0«. ? 

The solution of pyrotartaric acid in wood-spirit, saturated with dry 
hydrochloric acid ancf distilled over chloride of oalcinm and carbonate of 
magnesia^ yields a yellowish oil which sinks in water. (Arppe.) 



Pyrotartrate of Ethyl. 

Grunrr (1832) and Arppe in the memoirs cited on pa^es 83, 84. 
Malaouti. Ann. Chim, Phys, 64, 275; also Ann, Pharm. 25, 272; als 
J. pr. Chem. 11, 225. 

Pt'eparation, — A mixture of 1 pt concentrated hydrochloric acid^ 
i pts. pyrotartaric acid, and 4 pts. alcohol, is distilled to one>half; and 
the oily pyrotartrate of ethyl precipitated from the acid residue by water, 
washed repeatedly with water, digested with lead-oxide, and distilled. 
(Gruner.) 2. The solution of pyrotartaric acid in absolute alcohol is 
saturated with dry hydrochloric acid; evaporated a little; the compound 
ether precipitated by water in the form of a yellow oil; and this oil, 
after the watery liquid has been decanted, is neutralised with carbonate 
of soda, dried over chloride of calcium, and rectified. (Arppe.) — 3. The 
same process as for citric ether, excepting that hydrochloric acid is to be 
used in place of sulphuric, and the ether purified by distillation, — 
whereby it is but slightly decomposed^ — and washing. (Malaguti.) 

Properties, Transparent, colourless oil (yellow, according to Griiper); 
of sp. gr. 1*016 at 185°; begins to boil at 218°, but the boiling point 
rapidly rises in consequence of partial decomposition; smells like calamus 
aromaticus; has a pungent bitter taste (and burning, according to Graner); 
neutral (Malaguti). 

Malaguti. Arppe. 

18 C 108 .... 67*45 57-43 .... 57-40 

16 H 16 .... 8-51 8-67 ,.,. 8-71 

8 O 64 .... 34-04 33'S)0 .... 33-89 



C»HWO« 188 ..,. 100-00 100-00 .... 100-00 

DeeofnposUums. 1. The ether ia not set on fire by the flame of a 
eandle, but bums with a white flame when more strongly heated. It is 
scarcely attacked by chlorine, iodine or bromine« -— 2. It is decomposed 
by nitric acid, but only with the aid of heat. — 3. Dissolves, with slow 
decomposition in cold oil of vitriol, and when heated therewith, quickly 

{)rodnce8 sulphurous acid and charcoal. The solution in hydrochloric acid 
ikewise decomposes at SO''. (Malaguti.) — 4. It is slowly decomposed by 
water, more quickly by aqueous potash, into alcohol and pyrotartaric 



ANHYDROUS PTROTARTAKIC AGID. lOt 

acid. (Gruner^ Malaguti.) Dry ammoniacal gas has no action upon it; 
and no precipitate is produced by baryta, strontia^ or lime-water.— 
(Malaguti.) 

Combinations. — The ether is nearly insoluble in water, dissolves 
readily in cold oil of vitriol and hydrochloric acidj and in all proportions 
in ether and alcohol^ being precipitated from the latter by water. — 
(Gruner.) 



Onfysf^ nucleus C^<^H«0*. 

Anhydrous Pyrotartaric Acid« 

Abfpe. (1847.) De acido pp'otartarico, dhc, 20, 

Pyrotartaric Anhydride, Brenzweinanhydrid. 

Formation. 1. Pyrotartaric acid when boiled for Some time, loses ltd 
crystallisability, being for the most part converted into the oily anhy- 
drous acid, and if then distilled, yields, first water, then the anhydroud 
acid mixed with a small portion of the ordinary acid. — 2. Pyrotartaric? 
acid distilled with phosphoric acid, yields a distillate which, so long as nd 
carbonisation takes place, consists of the pure anhydrous acid. 

Preparation. I. Fused pyrotartaric acid mixed with glacial phos- 
phoric acid is distilled till the ]:e6idue begins to turn brownj[ pure anhy- 
drous pyrotartaric acid passing over all the while; tbd portion of the 
mixture which remains liquid after cooling is then decanted into another 
retort, ^nd about two- thirds distilled off at about 190°. 

Properties. — Colourless oil, which does not solidify at — 10°, sinks in 
water, boils at 280°, and volatilises nndeoomposed; inodorous at 20°, 
siitells like acetic acid at 40°; excites first a sweetish then a sour taste 
like that of the hydrated acid; when swallowed, it produces a burning 
and scratching sensation in the throat. Perfectly neutral. 



10 c 


, 60 


.... 52-63 .. 
5*26 .. 
.... 4211 


Arppe4 
, 62*65 


6 H 


6 


i,..,t 5'20 


6 O 


48 


42-15 








CWH»0« 


114 


.... 10000 .. 


100-00 



Decomposition. Converted slowly by water, quickly by aqueous 
alkalis, into ordinary pyrotartaric acid. 

Combinations. Dissolves very sparingly in wa/^*, readily in alcohol, 
whence it is precipitated by water in oily drops, which gradually change 
into thcf hydrated acid. (Arppe.) 



lOa AMTL: OXYGEN-NUCLEUS C»H«0<. 

Appendix to Pyrotartaric Acid, 

T. Bipyrotartrainide C»ffNO*. 

Arppb. Ann, Pharm. ST, 231. 

Bipyrtramidef Pffroiartrimide. 

Obtained by the dry distillation of acid pyrotartrate of ammonia 
(p. 87). To purify the crystalline product, wbich separates during the 
whole course of the operation, it is thoroughly moistened with water, 
dissolved by the aid of heat, left to separate by cooling, and pressed; 
and these operations are repeated till the yellowish colour is quite and 
the enip3rreumatio odour nearly gone; the odour may be completely 
removed by keeping the product for some time over oil of vitriol. 

Properties. Crystallises from solution in water, alcohol, or ether, in 
delicate shining anhydrous needles. — Impure bipyrotartramide, however, 
may remain liquid for a long time at the ordinary temperature of a room, if it containi 
but a trace of water, a peculiarity perhaps arising from the presence of an empyreu- 
matic oil ; but even in that case it soon solidifies when immersed in snow. — [Biffi 

obtained the compound in small white lamiuee which melted at the heat 
of the water-batn. {Ann. Phann, 91, 105).] The compound has a 
cooling, slightly bitter and sour taste. Melts at 66° to an oil which, on 
cooling, solidifies in a laminated crystalline mass, greasy to the touch. 
Volatilises at 100^ but does not begin to boil till heated above 280^ The 
boiling point is not constant. The aqueous solution has an acid reaction. 



Iv W •..II... 

N 

7H 


.... 60 

.... 14 

7 


.... 53*10 
.... 12*39 
.... 6*19 
.... 28*32 


Arppe. 

.... Oa 9v .... 

.... 12-60 

.... 0*1/ ....< 

.... 28*30 


Biffi. 
.... 53*1 

6*5 


4 


.... 32 





C«»NH70* .... 113 .... 10000 .... 10000 

Decomposition. Bipyrotartramide boiled with a large excess of strong 
solution of potash, gives off ammonia and forms pyrotartrate of potash. 

Combinations, — Dissolves in water; readily in the ordinary acids and 
alkalis; does not combine with ammonia. 

Lead-compownd. — Lead>oxide dissolves abundantly in an aqueous 
solution of bipyrotartramide, and the alkaline solution dries up to an 
amorphous mass, containing 5*47 p. c. (5 At.) water, which go off at lOO^i 
and not completely redissolved by water. 

Dried over oil of vitriol, Arppe. 

2 CWNH70< 226 .... 27*20 27*30 

6 PbO 560 .... 67-39 6723 

5 HO 45 .... 5-41 5-47 

C»'WH'0*,5PbO + 5Aq.... 831 .... 10000 100-00 

Bipyrotartramide does not combine with oxide of silver. 

Bipyrotartramide is soluble in oicokol and in ether, (Arppe.) IT. 



QUADRICULOROVALBRIANIC ACID. 103 



Chlonne-nucletis C^^^l'Hl 

Terchlorovalerianic Acid. 

Dumas & Stab. (1840.) Ann. Chim. Phyn, 73, 136; also Ann. Pharm. 
35, 149; AhoJ.pr. Chen^. 21, 283. 

Triehhrbaldriansdure, Aeide chlorovalerifique. 

Preparation, Dry chlorine gas is passed in the dark through dry 
valerianic acid, the liqnid being at first cooled with cold water, that it may 
not be thrown aboat, oat afterwards, when it begins to assume a more 
yiscid consistency, heated to 50° or 60°; the passage of the chlorine is 
continued as long as hydrochloric acid is evolved, and afterwards carbonic 
acid gas passed through the liquid as long as it drives out chlorine and 
hydrochloric acid. 

Properties. — Colourless, transparent oil, very thick at «- 18°, semi- 
fluid at ordinary temperatures, very mobile at 30 • Heavier than water. 
Inodorous; tastes sharp and burning, and makes a white spot upon the 
tongue. 

Dumas & Staa« 

IOC 60-0 .... 29-24 29*60 

3 CI 106-2 .... 51-76 50-80 

7 H 7-0 .... 3-41 3M5 

4 32-0 .... 15-59 16-15 

C^CPIFO^., 205-2 .... 100-00 100-00 

Decomposition. — The acid gives off a large quantity of hydrochloric 
acid between 110° and 120°. 

Comhinadions. The acid takes up water immediately, and forms a 
venr fluid hydrate, which sinks in water, and does not give off the whole 
of its water even at 100° in vacuo. 

From its solution in [concentrated ?] alkalis, it is precipitated by 
stronsrer acids. 

The recently-prepared dilute aqueous solution does not precipitate 
nitrate of silver; but the hydrate forms with it a copious precipitate, 
perfectly soluble in nitric acid. (Dumas & Stas.) 



CJUorine-nucleus C**C1*0^ 

Quadrichlorovalerianic Acid. 

C^»C1*H«0* = C^^C1*H«,0* 

Dumas & Stas. (1840.) Ann, Chim. Phys. 73, 139; also Jni?. Phaiin. 
35, 150; also J. pr, chem. 21, 285. 

Quadriehlorbaidriant&ure, Aeide chlorovalerosique. 

Preparation. Dry chlorine gas is passed in sunshine, through dry 
valerianic acid, at first in the cold, afterwards at 60°, till the formation of 



lOA AMYLENE : CHLORINE-NUCLEUS C»a<H«. 

hydrocbloric acid ceases, and afterwards carbonic acid gas passed through 
the liquid for several hours to expel the free chlorine and hydrochloric 
acid >Yhich colour the acid yellow. 

Properties Colourless, semi-fluid oil, which does not soldify at — 15°; 
heavier than water ; not volatile ; inodorous ; and haying a burning, 
^mewhat bitter taste. 



10 c 


60-0 


.... 25-04 
.... 5910 
.... 2-50 
.... 13-36 


Daman Sc Stas. 
24-97 


4 CI 


141-6 


59-10 


6 H 


60 


2-59 


4 


32-0 


13-34 









C»0Cl*H«O* 239-6 .... 100-00 100-00 

Deeom/posUums. 1. In the dry state, the acid remains unaltered at 
ordinary temperatures aud at 1 50'^, but decomposes at higher tempera* 
tures, with evolution of hydrochloric acid. — 2. It is not decomposed by 
ammonia, but auickly by excess of potash or sod% with formation of a 
chloride and a brown substance. 

Comhinatwns, The acid shaken up with a small quantity o£ water 
forms a thin oily hydrate and above it an aqueous solution. — a. The 
hydrate becomes turbid at — 18°, with separation of ice. It decomposes 
with formation of hydrochloric acid, when heated, and even when merely 
left at rest for several days, so that it then precipitates nitrate of silver. 
It contains 233 p.c. C and 3*1 H, and is therefore C^^C1«H<>0S 2 HO. 

h. In a large quantity of water, both the acid and its hydrate are 
abundantly soluble. 

The Quadrichlorovalerates or Chlorovalerosatet = C*®Cl*H'MO*. The 
acid expels carbonic acid from the alkaline carbonates ; its ammonia, 
potash, and soda-saMs taste very sharp aud bitter, and from these solutions 
[when not too dilute], stronger acids throw down the hydrate. 

By precipitating nitrate of silver with the ammonia-salt, quadrichlo- 
rovalerate of silver is obtained as a white crystalline precipitate. This 
salt is gradually decomposed in the dark into white chloride of silver, 
and a substance which spots paper and is perhaps C'^Cl'H'O^ [more 
probably: C^^CPH'O*]. The silver-salt dissolves sparingly in water, 
readily in nitric acid; and these solutions, when exposed to light^ deposit 
black chloride of silver. 

Jhied, 

10 C 

401 

5H 

Ag 1080 

4 O 32-0 

C»»Cl<H*AgO< ....; 346-6 .... 100-00 

The acid dissolves readily in alcohol and ether-j but the solutions^ after 
a while, precipitate nitrate of silver. (Dnmas & Stas.) 







Dumas & Stas 


60-0 


.... 17-31 


170 


141*6 


.... 40-86 




50 


.... 1-44 


1-5 


1080 


.... 31-16 


31-6 


32-0 


.... 9-23 





AMYLAMINE. 105 



Amidogenrnuclew C^^AdH*. 

Amylamine. 

C"NH" =: C"AdH*,H» 1 

WuRTZ. (1840.) Compt. rend. 29, 186; also J^. J. Pharm. 16, 277.— 

y, Ann. Chim. Phyt. 30, 447. 
Brazieb & GossLBTH. Chem. Soe. Qu. J, 3, 210; Ann. Pharm. 75, 252. 

Amyliaque, Vaieraminef Ammonia^ne vahripte. 

Formaiton. 1 . In the decomposition of cyanate of amyl (aUophanate 
of amyl, — p, 74) cyanurate of amyl, or amyl-urea by potash : 

C«NH"0« 1- 2H0 + 2KO - C»»NH» + 2(K0,C0«) ; 
and C»N«H«0> 4- 2H0 4- 2KO -= C»NH» + 2(KO,CO») + NIP. 

T. 2. By heating tmylosalphate of lime with alcoholic ammonia : . 
CWH»Ca,2S0< + NH» - C^NH^ HSCH + CaSO*. 

The mixture heated to 250^ for two hours in a sealed tube, yields a mass, 
which when distilled with potash, ^yes off amylamine. Amylosulphate 
of baryta appears to act in a similar manner. (Berthelot, 0<mpt. rend, 
36, 1098.) IT. 

Preparation, Cyanate of potash is distilled with amylosulphate of 
potash; the resulting distillate of cyanate and cyanurate of amyl again 
distilled with strong caustic potash, the cyanurate of amyl being decom^ 
posed after the water has passed over; the strongly alkaline distillate, 
which oflen consists of two layers, neutralized with hydrochloric acid, 
filtered, and evaporated on the water-bath; the bydrochlorate of aniy« 
lamine which remains, purified by recrystallisation and distilled with lime; 
and the amylamine which passes over, rectified by distillation over 
baryta or hydrate of potash. (Wurtz.) Since cru((e cyanide of amyl 
(p. 67) when prepared from cyanide of potassium containing cyanate of 
potash, is contaminated with allophanate of amyl, it follows that when 
such impure cyanide is boiled with alcoholic potash to obtain caproate of 
potash, the alcohol and fusel-oil which pass over are accompanied by 
amylamine; and consequently, when the distillate, after being mixed 
with hydrochloric acid, is evaporated to a syrup, this syrup diluted witli 
water, whereupon an additional portion of fusel-oil separates out, and 
the liquid separated therefrom boilod for a while to expel the rest of the 
fusel-oil, a liquid is obtained, which, when subsequently distilled with 
potash, yields pure amylamine. (Brazier & Gossleth.) 

Propertiea. Colourless, yery thin liquid, of sp. ffr. 0*7503 at 18°, 
boiling at 05°^ smelling of ammonia and fusel-oil, and having a burnintr, 
<»aBtie and bitter tasie. (WorU) Boils at 93^ (Brasierek Gossleth^). 



109 AMYLENE: AM lOOG EN-NUCLEUS C^AdH*. 



IOC 

N 

13 H 





Wurtz. 


60 .... 08-97 ... 


68-52 


14 .... 1609 




13 .... 14-94 ... 


1503 



C^NH" 87 .... 100-00 

Dfcompositmis. 1 . Amylamine barns with a bright flame. ^Wartz.) — 
2. With bromine it forms hydrobromate of amylamine ana insoluble 
drops of a bromine-compound. (Wurtz.) — 3. Supersaturated with 
hydrochloric acid and gradually dropt into a warm aqueous solution of 
nitrate of potash, it gives off a large quantity of nitrogen and yields an 
oily distillate of nitrite of amyl. 

CWNH" + 2NO» = CWNH"0* + 2H0 + 2N. (Wurti.) 

At the same time, however, there are formed a few easily fusible laminas 
having a fatty lustre, which partly distil over with the amylic nitrite 
and afterwards separate from it, partly remain behind with the chloride 
of potassium. (Hofmann, Ann Fharm. 75, 864.) 

ComJlnnatiom, Amylamine mixes in all proportions with toater, 

SdUs of Amylamine, — The following bases are precipitated irom 
their solutions in acid by amylamine : Magnesia, alumina, the sesqui- 
oxides of chromium and uranium, protoxide of manganese, the teroxides 
of antimony and bismuth, oxide of zinc, oxide of cadmium, protoxide 
of tin, protoxide of lead (from nitric but not from acetic acid), sesqni- 
oxide of iron, the protoxides of cobalt, nickel and copper, mercurous 
oxide, corrosive sublimate (white precipitate^, oxide of silver, and 
teroxide of gold; an excess of it redissolves alumina^ oxide of copper, 
oxide of silver, and oxide of gold. (Wurtz.) 

Carbonate of Amylamine. — Formed as a crystalline deposit on the 
sides of vessels containing amylamine and exposed to the air. • 

Sulphate of Amylamine. — Formed by heating amylosulphate of lime 
or baryta with alcoholic ammonia. (Berthelot, p. 58.) 

Hydrobromate of Amylamine. — Melts at a strong heat and diffuses 
white inflammable vapours. Permanent in the air, very soluble in water 
and alcohol, very sparingly in ether, which precipitates it from concen* 
trated alcoholic solutions. (Wurtz.) 

CryttaU, ^ Warts. 

IOC 60-0*.... 48-62 48-2 

N 140 .... 11-35 

14 H 140 .... 11-35 11-4 

CI : 35-4 .... 28-68 28-3 

CWNH»»,HC1 123-4 .... 100*00 

Amylamine in excess redissolves alumina precipitated from its salts 
by a smaller quantity of amylamine (a property which may be made 
available for the separation of alumina from sesquioxide of iron); also 
cuprie oxide with azure colour, but not so readily as ammonia; also, bat 



BIAMTLAMINE. 107 

without coloar and only when in great excess^ the tawny resinous preci- 
pitate which a smaller ^antity of amylamine produces in nitrate of 
$Uver; and the yellow-brown gnmmy precipitate which it forms in soltUion 
of ffold. It also dissolyes chloride of silyer, but not so readily as 
ammonia. (Wurts.) 

PlatinuirhmU, — Hydrochlorate of amylamine and bichloride of 
platinum^ mixed in concentrated aqueous solutions^ with addition of a 
little alcohol, yield a precipitate, which, after being collected on a filter 
and pressed, separates from solution in boiling water in golden yellow 
scales. (Wurtz.) 



IOC 




.... 60-0 


.... 20-46 ..., 
.... 4-78 

• ••• 4 / O ■■•! 

.... 33-76 ... 
.... 36-22 ... 


Worts* 
20-47 .. 

4-85 .. 

32-60 .. 

35-88 


Braderft 
GonliBth. 
20-30 


N 

14 H 




.... 140 
.... 14-0 


•••••• V ^^w 


Pt 

3 CI 




.... 990 
.... 106-2 


33-45 










C»0NH" HCI + 


PtCP 


... 293-2 


.... 100*00 







Amyloxamide, — Amylamine in contact with oxalate of ethyl becomes 
strongly heated, and solidifies in silky needles. These crystals melt at 
139°; Tolatilize without residue at a stronger heat, difiiising white 
vapours; are insoluble in water; but dissolve in boiling alcohol, from 
which they separate almost completely on cooling. (Wurtz). [The mode 
of formation is probably as foUows] : 

C12HW08 + 2(CMNHM) - C«N«H2«0* + 2(C*HHy.) 



% Biamylamine« 

C«^NH» = C'»Ad(C**H")H»,H*. % 

A. W. HoFMANN. Phil. Tram. 1851, II, 357; Ann. Pharm. 79, 20; 
Chem. Soc. Qu. J. 4, 322. 

Dtomy/amin^. —May also be regarded as (CU»HU»)3,H>N, or as (CioH»}*H,N. 

Formed as a hydrobromate by the action of bromide of aroyl on 
amylamine. The action takes place slowly in the cold, rapidly at 
100^ The resulting white crystalline mass decomposed by potasli yields 
the base. 

Biamylamine when pure is a light oily liquid, which boils at about 
170^ has a peculiar though not unpleasant odour, like that of amylamine, 
and a hot pungent taste. It is but very sparingly soluble in water, to 
which however it imparts an alkaline reaction. 

Biamylamine combines with acids, forming salts which dissolve but 
sparingly in cold water, but may be recrvstallisedfrom boiling water. The 
Hydrochlorate is nearly insoluble in cold water; its warm solution forms 
with bichloride of platinum a beautiful PkOinum-iolt, which dissolves 



108 AMYLENE : AMIDOGEN-NUCLBUS CMAdH«. 

preity easily in water, and often separates from tke solatioA in oilj drops 
which gradually solidify in the crystalline form. 

Bpdrochhrute4 Hofmand. 

C»NH« 157-0 .... 81-19 

HCl 36-4 .... 18-81 :.. 18-51 

C»NH» HCl lW-4 .... lOO-OQ 

Platinum'Sait, Hofmum. 

0"NH« 193-4 .... 63-26 

2 CI 70-8 .... 19-49 

Pt ^ 99-0 .... 27-25 27-10 

C»NH= HCl,PtCl« .... 363-2 .... 10000 



• 



f. Metethamylamine. 

C^«NH" = C"Ad(C»H»)(C*H»)H',H». 1 

A. W. HoFMANN. Ann. Pharm, 78, 285; Chem. Soc, Qu. J. 4,317. 

Meih^Mhfflamyldmine, JFbrmovmamjffamt'nff. — Maj bt regarded as 
(C«H2)(C*H^)(CWHW),NH3, or as (C2HS)(C«H*)(C^H")N. 

Obtained by the dry distillation of hydrate of methylobiethamylamine 
(p. 110), water and olefiaut gas being given off at the same time : 

C»NH»,2H0 m C^NHW + 2HO + C«H*. 

Transparent oil, having a fragrant odour and similar taste. Dis- 
solves sparingly in water, to which it imparts an alkaline reaction. 
After being dried over hydrate of potash and rectified, it boils constantly 
at 135°. ^ • 

Dissolves slowly in acfds. The hydrochlorate forms with bichloride 
of platinum, a double salt which is very soluble in water, and is usually 
precipitated on mixing the two salts in strong solution, or on evaporating 
\he mixture, in deep orange^yellow oily globules, which gradually 
solidify in magnificent needles. 

Platimtm'ialt. Hofmann. 

C^NHW 165-4 .... 49-35 

2 CI 70-8 .... 21-13 

Pt 99-0 .... 29-52 29-36 



.^-^-^— ^— — i^.^B<— •^•..mAa. 



Ci«NHW HCl,PtCl« .... 335-2 .... 10000 

^« Biethamylamine. 

C"NH«^ = C'^Ad(OH»)»H\H* 1 

A. W. Hofmann. Ann. Pharm. 78, 282; Chem, Soc. Qu. J. 4, 315. 

Diethamtflamine, Bhinamyhmine.^'HrLj also be fCMrded as rC*H«)*(C»H»0),Na», 
or as (C*H»)«tC>«H")N. , ^ . / v y» » 



TRUMTLAMINE. 109 

Obtained, together with water and olefiant gSLS, by the dry distillation 
of hydrate of triethamylamine (p. 111). — Oily liquid, heavier than water, 
having a not unpleasant odour, and an analogous, somewhat bitter taste. 
After drying over hydrate of potash, it boils oonstantly at 1 54°, which 
is just 19° higher than the boiling point of metethamylamine (p. 108), 
agreeing therein with Kopp's law (vii, 55), 

Biethamylamine is less soluble in water, and combines less readily 
with acids than metethamylamine. The Sulphate, HydrocIiloraU, Nitrate, 
and Oxalate crystallise readily, but are deliquescent. The Plaiinuwrsdii 
separates on cooling from a concentrated mixture of the hydrochlorate 
wilh bichloride of platinum^ in orange-yellow needles of extraordinary 
beauty. 

Plaiiwunir9aH, Hofmann. 

CWNHn,HCl 179-4 .... 61-87 

2 CI 70-8 .... 20*27 

Pt 99-0 .... 28-36 28-03 

Ci8NH2SHa,PtCl« .... 349-2 ..,. 100-00 



^. Triamylamine. 

C^XH" = C*^Ad(C»oH")»H^H». 1 
A. W. Hofmann. Ann. Pharm, T9, 22; (Mem, Soo* Qu* J* 4, 323. 

May aUo be regarded as (CWHW)3NH3, or a« (C»<>H")»N. 

Obtained : 1. By the action of bromide of amyl on biaroylamine.—- 
2. By dry distillation of hydrate of tetramylamine (p. 111.) Resembles 
biamylamine in most of its properties. Boils at 257°. 

The Hydrochlorate separates immediately as a nacreous crystalline 
mass, on mixing the base with strong hydrochloric acid; and on adding 
bichloride of platinum to the solution, the Platinum-salt separates as a 
viscid masSj which gradually solidifies in the crystalline form. 

Hydrochlorate. Hofmann. 

C»NH» 227-0 .... 86-18 

HCl 36-4 .... 13-82 13-73 

C^NH^UCl 263*4 .... 100-00 

Platinum-salt, Hofmann. 

C»NH» HCl 263-4 .... 60-80 

2 CI 70-8 ,... 16-35 

Pt 99-0 .... 22-85 22-82 

C»NH» HCl,PtCl« .... 433-2 .... 10000 



110 AMYLENE: AMIDOGBN-NUCLEUS C»AdH». 



n. Methylobiethamylamine. 

C^NH« = C»«Ad(C»H»)(C*H»)«,H«,H». ? * 
A. W. HoFMANN. Ann. Fkaim. 78, 283; C^icTn. Soc. Qu. J. 4, 316. 

Supposing it to contain 1 At H more, it may be regarded as Meihyiobietkylamyl- 
ammamum - C*H»,(C*H»)8,C»H",N. 

Known only in combination with water and acids. 
Obtained as a hydriodate by the action of iodide of methyl on bieth- 
amylamine. 

[C»NH«» + C»H«I = C«NH« HI or C?oNH« I.] 

The methylic iodide most be added gradaally ; for on suddenly mixing, a 
violent action takes place and the liqaid is projected with a kind of 
explosion : it is best also to make the mixture in a tubulated retort pro- 
vided with a condenser. The mixture on cooling solidifies into a hard 
white crystalline mass of the hydriodate, This salt is very soluble in 
water, and forms a very bitter solution from which it is reprecipitated by 
potash in oily globules which solidify but slowly. 

The hywodate digested with oxide of silver, yields the hydrate of 
methylobiethamylamine, C^NH^,HO [or hydrated oxide of methylodi- 
ethylamylammonium : (C'H'),(C*H*)»,fCi»H"),NO] in the form of a 
strongly alkaline solution, which, wnen evaporated to dryness, and 
distilled, is resolved into water, defiant gas and metethamylamine: 

C^'NHa^HO « C<H< + HO + CWNH» 

The hydrate forms crystalline salts with sulphuric, hydrochloric and 
nitric acid. The hydrochlorate mixed with bichloride of patinum forms 
a beautiful platinum-salt. 

Hofmann. 

C«NH»,Ha 193-4 .... 53-25 

2 CI 70-8 .... 19-49 

Ft 99-0 .... 27-26 27*29 

C?»NH» HCl,PtCl« .... 363-2 .... lOO'OO 
or: (C*H>)(C«H»)»(C»HM)N,a,Pta«. (Hofinann.) 



* Thifl and the similar formulse for the other amyl-baies containing 4 At. of the 
alcohoUradicals (pp. Ill, 112) are given in accordance with those assigned by Gmelin 
to the corresponding bases of the phenyl-series (g, v,) ; but there can be little doubt 
that the formnlsD originally given by Hofmann accord much more nearly with the 
observed chemical relations of these compounds.— [Tr.] 



TRIETHAMTLAMfNE. Ill 

IT. Triethamylamine. 

C«NH« = C^<^Ad(C*H»)»H«,H« ? 
A. W. HoPMANN. Ann, Fharm, 78, 279; Cheni, Soe. Qu. J. 313. 

Sapposing it to contain 1 At. H more, it may be reg^arded as TV-iel^ylamyiammamum 
= (OH»)»,C»0H»,N. 

Known only in combination with water and acids. 
Obtained as a hydriodate by the action of iodide of amyl on triethy- 
lamine. 

C»NH« + CWH»I « C»NH»,HI. 

The action is not very rapid, and to complete it, the miztare must be 
heated in a sealed tube for two or three days. 

The solution of the hydriodate boiled with oxide of silver yields the 
UjfdrcUe C«NH», HO [or the oxide of triethylamylammonium C*«NH« 0] 
in the form of an alkaline solution having an extremely bitter taste. Ou 
evaporating this solution, the hydrate remains in the form of a syrnp 
which does not show any disposition to crystallise. When distilled, it 
yields water, defiant gas and biethamylamine : 

C«NH» HO « HO + C<H< + CWNH". 

The Sulphate and Oxalate of triethamylamine, when evaporated in 
vacuo, leave a syrupy or gummy residue like the base itself. 

The Hydriodate forms very fine crystals, which exhibit the fatty 
lustre and touch peculiar to the amyl-compounds. It dissolves with great 
facility- in water and alcohol, but is insoluble in ether. The solutions 
have the bitter taste of quinine. On the addition of potash or carbonate 
of potash, the hydriodate separates in the form of an oil, which rapidly 
shoots into brilliant needles. The salt when slightly moist, melts at 
100° to a clear oily liquid, which becomes solid when cold and perfectly 
dry, and gradually turns yellow. 

Hofmann. 

C»NH« 171 .... 57-39 

HI 127 .... 42-61 42-66 

C«NH«HI 298 .... 100-00 

The EydrocMorate forms very deliquescent laminae; the Nitrate^ hard 
permanent needles having a cooling taste. 

FlalinunirMU. The solution of the hydrochlorate is not precipitated 
by bichloride of platinum, except when highly concentrated; but the salt 
when once formed, is much less soluble. From a boiling aqueous solution 
it shoots out in splendid orange-yellow needles, sometimes half an inch 
long. 

HofmaoD. 

C«NH« HCl 207-4 .... 54-98 

2 CI 70-8 .... 18-77 

Pt 99-0 .... 26-25 25-76 

C»NH»,HCl,PtCl« .... 377-2 .... 10000 



HS AMYLENE; AMIDOGEN-NUCLEUS CWAdU'. 

The deficiency in the platinum determination appears to be dne to a peculiar 
decomposition which the platinum -salts of these bases undergo when their solutions are 
boiled; the salt in this instance had been recrystallised from boiling water. The 
decomposition in question cannot be discovered by any change of appearance, but only 
from the diminution in the amount of platinum. (Uofmann.) 



IT. Tetramylamine. 

C*»NH« = C»Ad(C»^H*7H»,H«. ? 
A. W. HoFMANN. Ann. Fharm, 79, 24; Chenu Soe. Qu, J, 4, 324. 

Supposing it to contain 1 At. H more, it may be regarded as Tetramylammonium 
6r TetrttmyliuM - (C»»HW)*,NH* or (C»»H")SN. 

Known only in combination with water or acids, 

It is obtained as a hydriodate: 1. By the action of iodide of aniyl 
on trianiylamine, the mixture solidifying after three or four days' boiling 
into an unctuous crystalline mass. — 2. By heating iodide of amyl in a 
sealed tube with strong solution of ammonia. Tlie action is however very 
slow, not being complete even after several weeks' boiling. The excess 
of iodide of amyl may be removed by distilling the liquid pe7' se, and the 
ammonia and the lower amyl-bases by distillation with potash ; the 
hydriodate of tetramylamine then remams in the form of a heavy oil 
which on cooling solidifies in a mass having the consistence of stearin. It 
dissolves sparingly in water, forming an extremely bitter liquid, from 
which it is re-precipitated in the crystalline form by alkalis. When dry 
it assumes a pale yellow colour. 

Hofmann. 

C«NH« 297 .... 70-05 

HI 127 .... 29-95 29'74 

C«NH« HI 424 .... 100-00 



On boiling the hydriodate with oxide of silver, there is fonned a very 
bitter alkaline solution o£ hydrate of tetramylamine [or oxide of tetramylium]. 

C«NH« HI + AgO - Agl ^ C«NH« HO. 

This base is less soluble in water than the corresponding methyl and 
cjthyl-compounds (vii, 320; ix, 66). On adding potash to the solution, 
the base rises to the surface in the form of an oily layer. The aame effect 
takes place when the solution is strongly concentrated by evaporation; in 
the latter case, the oil gradually solidifies into a crystalline mass. A 
moderately concentrated solution of the base, left to evaporate in an 
atmosphere free from carbonic acid, deposits after a while, magnificent^ 
perfectly definite crystals, sometimes an inch in length and thickness; 
they are but moderately deliquescent, and attract carbonic aoid from the 
air but slowly. These crystals consist of the hydrate of tetramylamine 
with several atoms of water of crystallisation. When heated, they melt 
in their water of crystalUsation, and on evaporation in the water-bath. 



VALERAMIDE. 113 

leave a semi-solid transparent mass consisting of the pnre hydrate. 
This hydrate is decomposed, partially at the heat of the water-bath, 
completely at higher temperatures, into triamylamine, water^ and a 
hydrocarbon^ which is probably amylene : 

C«NH« HO - C»NH» + HO + C»H«», 

Svlphaie of Tetramylamine crystallises in long, capillary threads; the 
Nitrate in needles; the Oxalate in large, well-developed plates, which are 
extremely bitter and deliquescent; the ffydroeMorate crystallises in leaves 
with palm-like ramifications. Its solution forms with chloride of platinum 
a pale yellow curdy precipitate which gradually solidifies in beautiful 
orange-yellow needles. 

Hofmann* 

0«NH«,Ha 333-4 .... 66*25 

2 CI 70-8 .... 1408 

Pt 990 .... 19-67 19-63 

C«NH« Ha,PtCl2 .... 603-2 .... 100-00 
or: C^ONH<<Cl,PtCl « (C»H")<N,Cl,PtCP. (Hofmann.) T. 



Valeramide. 

(?»NH"0* = C^«AdH«,0*. 

Dumas, Malaouti & Leblanc (1847). Compt rend. 25, 475, 

and 658. 
Dessaionbs & Ghautard. iT. J. Pharm. ld> 245; also J. pr. Chtm. 

45, 48. 

Formation and Preparaiion» Bv placing valerate of ethyl in contact 
with aqueous ammonia. (Dumas, &c!) — 1 vol. valerate of ethyl set aside 
with 8 vol. concentrated ammonia in a closed bottle and frequently 
shaken, requires four months in summer to disappear; and the liquid, if 
then evaporated at a gentle heat, leaves crystalline valeramide. 
(Dessaignes.) 

Large, thin, shining lamiuss which melt at 100^, and immediately after- 
wards sublime in very delicate, iridescent laminss. NeutraL (Dessaignes 
& Chautard.) 

Dessaignes & Chautard; 

IOC 60 .... 69-41 60-05 

N 14 .... 13-86 

11 H 11 .... 10-89 10-94 

2 16 .... 15-84 

CiONH"0» 101 .... 10000 

Deeompotiiions. 1. Valeramide heated with anhydrous phosphoric 
acid, is resolved into water and valeronitrile. (Dumas, &c.) So likewise 
when its vapour is passed over red-hot lime. (Hofmann.) 

CiONH"OS - 2H0 + C*«NH». 
VOL. XI. I 



} 14 AMTLENB : AltflDOOBM-MUCLEUS CVAdH*. 

9. With poUsh-ley at the boiling heat» it gires off a small qoaottty 
of ammonia. (Deasaignes & Chaatard.) — 3. Heated with potaanom, it 
yields cyanide of potassium, hydrogen gas and a gaseous hydrocarbon. 
(Dumas, &c.) 

Cambinatum. — Valeiamide dissolves rery easily in water. (Des- 
saignes and Chaatard.) 



Amylnrefhane. 

C»NH»0* = C"AdH",2C0«. 

Mbdlock. Chem. Soe. Qu. J. 2, 252 ; also Ann. Phamt. 71, 104. 
WuRTZ. JV. J. Pharm, 17, 79. 

Carbonate qfAmyl, Kohknmjfl ammt er, VreihamyUme. 

Preparation, Chloroformiate of amyl (p. 66), is mixed with aqueous 
ammonia, and the oil which rises to the surface and solidifies into a ciys- 
talline mass of amylnrethane and sal-ammoniac, freed from fusel-oil by 
pressure between paper, and from sal-ammoniac by washing with water 
till the liquid which runs through no longer precipitates nitrate of silver. 
(Medlock.) — 2. The compouna is also obtained by the action of chloride 
of cyanogen on fusel-oil. (Wurtz.) 

C»H>H)« 4. C«Na + 2H0 - C"NHMO* + HQ. 

ProperUa. Amylnrethane separates on cooling from its solution in 
hot water, alcohol, or ether, in silky iridescent needles, which melt at 
60*^, distil over without change at 220^, and solidify in the neck of the 
retort into a crystalline mass having a fatty lustre. (Medlock.) 



N 


(.... /• 


.... 54*96 ... 
.... 10-69 ... 


Medlock. Wartc. 

65*11 .... 54*81 

10'70 .... 10*71 


12 H 


13 


9-93 .... 10*08 


4 O 


o« 


24*26 .... 24*40 


CMNH"0< 


181 


.... 10000 ... 


100*00 .... 100*00 



Deeampotitiani. ^ The solution of amylnrethane in oil of vitriol is 
resolved by heat into carbonic and sulphurous acid gases, sulphate of 
ammonia, and amylosulphuric acid. [According to the equation; 

C"NH»0* + 4S0» + 2H0 - C»H"0»,2S0" + NH»,2SO« + 2C0». 

there should be no sulphurous acid produced ; it is perhaps formed by 
further decomposition of the amylosulphuric acid by the excess of oil of 
vitriol]. — 2. When amylnrethane is distilled with baryta, carbonate of 
baryta is formed, and ammonia and fusel-oil (but no valeramine) pass 
over. (Medlock.) The 2 HO required to form these products must be 
derived from another decomposition of a portion of the amylnrethane. 
(Medlock.) 



SmCALINB, ^115 

Cmkbifuaims. — Amylaretliane dissolves in boilinff water. 
It dissolves in cold aU of vUriol, and on addition of water rises to tbe 
sanaoe onaltered, and forms a crystaUine crnst. 
Dissolves in o^ooM and 0(A^. (Medlock.) 



Ozamylane. 

C"NH«0« = C»oAdH»,C*0« ? 
Balard. (1844.) Ann. Chim. Phys. 12, 309; also J, pr. Chem. 34, 141. 

Ol^tained by the action of dry ammoniacal gas on oxalate of 
amyl (p. 72). 

Separates from its alcoholic solution in indistinct ciystals. 
Resolved by boiling with water, and more qnickly with aqueoas 
alkalis, into fusel-oil and oxamic acid (ix, 259). (Balard.) 



f- Sincalme. 

C'0NH"O» = Ci°AdH",0». 
Babo k HiRSCHBRUNN. Ann. Pharm, 84, 10. 

Formatum, By the action of alkalis on sinapine, the alkaloid contained 
in white mustard : 

C»NH«OM> + 2H0 - C»0NH»O> + C«HM0M. 

sinapine. dncaline. sinapic acid. 

Preparation, Hydrosulphocyanate of sinapine is heated with baryta- 
water till the whole of the sinapic acid is extracted in the form of a 
barytap^t; the filtrate acidulated with sulphuric acid and mixed with 
sulphate of copper and protosulphate of iron to precipitate the hydrosul- 
phocyanic acid; an excess of baryta added to remove the sulphuric acid 
and the excess of iron and copper; the baryta removed by passing car- 
bonic acid gas through the liquid; the carbonate of sincaline, which then 
remains in solution, converted into a hydrochlorate; this salt decomposed 
by digestion with oxide of silver; and the filtrate evaporated over the 
water-bath or in vacuo. 

Properties. Crystalline mass, oolonrless or slightly brown. 

Decomposiiion. Sincaline cannot be volatilised without alteration; 
when distilled, it gives off combustible vapours having the odonr of 
methylamine, and leaves a carbonaceous residue. 

Combinations. Sincaline dissolves in vfoter; when exposed to the air 
it becomes heated, deliquesoes> and la converted into a caroanaU. 

t 2 



116 AMTLENE: AMIDOGBN-NUCLEUS C>oAdH«. 

It dissolves 9fidphur: and on addinff a mineral acid to the solution^ it 
fives off salphnretted hydrogen, and deposits solphury which renders the 
liquid milky. 

Siucaline precipitates most metallic oxides from their solutions, not 
excepting lime, baryta, and mercuric oxide. The precipitates which it 
forms in salts of alnmina and of chromic oxide, redissolre in excess, and 
the chromic oxide is reprecipitated on boiling the solution. 

Gold'SaU. — Precipitated on mixing hydroehlorate of sincaline with 
terchloride of gold, in the form of a yellow crystalline powder, which is 
but sparingly soluble in cold water. It dissolves in boiling water, and 
crystallises on cooling, in the form of needles grouped in tufts. 



10 c 


Dried at llO''. 
60-0 


1 Bthi 

.... Xw 4*f .... 

.... 3-15 
.... 3-10 .... 

44*77 
.... 31-85 
.... 3-59 


& Hinchhroi 
.... 13-63 


N 

14 H 


14-0 

14-0 


..*• o'Ao 


Aa ... . 
4 a 


199-0 

141-6 


.... 44-54 


2 O 


16-0 











CWNH»0»,HCl,AuCl»... 4446 .... 100-00 

Platinum-saU. — Obtained in splendid orange-coloured prisms or six- 
sided tables, by evaporating a mixture of hydrochlorale of sincaline and 
bichloride of platinum. 

Dried ai 110^ Babo & Hinchbnum. 

IOC 60-0 .... 19-39 19-65 

N 14-0 .... 4-52 

14 H 140 .... 4-62 5-13 

Pt 990 .... 3200 31-36 

3 CI 106-4 .... 34-40 

20 160 .... 517 

C«>NH»0«,HCl,PtCl«,... 309-4 .... 10000 

Bubo & Hirschbninn suppose sincaline to contain 1 At. H more than Is here 
assigned to it, making the formola C^^^NH^^O*; this agrees rather better with the 
analysis of the gold and platinam*salts, making the hydrogen in the former 3*36 p.c, 
and in the latter 4*83 ; bat it is improbable, because it gives an nneven number for the 
sum of the numbers of atoms of N and H. \md, Gerhardt, TraiU de Chimie oraanique, 
2, 430.) T- 



f . Xanthamylamide. 

C"NH"SW = C"AdH",CS»,CO«. 

M. W. Johnson. Chem. Soc. Qu, J. 5, 142; abstr. Ann. Pharm., 84, 836; 
iT. Ann. Chim. Phys, 36, 361; JahreBher. 1852, 605. 

Produced, together with amyloxanthate of ammonia, by the action of 
ammonia on bioxysulphocarbonate of amyl (p. 62). 

2C"U»S<0« + 2NH» " C>SNH»S»0« + CWH"(NH*,)0«,2CgP + 23. 



XANTHAMYLAMIDE. 117 

The bioxysulpfaocarbonate of atnjl is digested at a gentle heat with 
stroDff aqueous ammonia, whereupon sulphur quickly separates out, and 
a yellow liquid is produced with oily particles suspended in it; and the 
solution of amyloxanthate of ammonia thus formed is passed through a 
wet filter, which retains the oily liquid together with the sulphur. The 
oily liquid, which is the xanthamylamide, is then washed with water, 
and separated from the sulphur by means of a dry filter, and dried, first 
in vacuo over sulphuric acid, afterwards more completely by passing a 
stream of dry carbonic acid gas through it at a gentle heat. 

The process which was adopted with advantage hj Debas in the preparation of 
xanthamide (iz, 276), viz., passing dry ammoniacal gas into the alcoholic solation of 
the biozysolphocarbonate, evaporatingi and treating the residue with ether to separate 
the amide from the ammonia-salt formed at the time, was fonnd not to be applicable to 
the case of amyl-oompoand, because the amide and the amylozsnthate of ammonia are 
nearly eqnaDy solnble in ether. 

Properties. — Yellow oily liquid neutral to test-paper. Boils at 184°, 
bat not without decomposition. 



12 C 


72 


.... 9'52 

•.M 21*77 .•• 
.... 10*88 


Johnson. 
49*24 


N 


14 




13 H 


1^ 


..... 10*04 


2 S 


32 


..... 20-91 


2 


1ft 




C^H^S*©" 


>•...••••. X4/ 


.... 100*00 





The analytical numbers are only approzimatife, became the compoimd oould not be 
purified by distillation. 

Deo(mpo9Ui<ms. 1. Xanthamylamide is xesolTed by distillation into 
amylio mercaptan and oyanuric acid : 

3C»NH»S«0* - 3CWH»S> + (WHW. 

When heated on platinum-foil, it gives off white yaponrs and bums with 
a yellow luminous flame. — 2. When boiled with hydrate of baryta> it is 
lesolyed into amylic alcohol and sulphocyanide of barium, ammonia being 
however eyolved at the same time : 

C«NHMS»0* + BaO.HO - CP^WH^ + C«NBaS« + 2H0. 

[This equation does not account for the cTolution of ammonia ; did it arise from an 
impurity ?] Potash exerts a similar reaction. — 3. Chlorine'toater decom- 



poses the compound, with separation of sulphur and formation of volatile 
oil. Hydrochloric acid has no action upon it, even at a boiling heat. -— 
4. Fummg nitrie acid acts violently upon it, giving off red vapours, and 
water added to the solution causes the separation of oily drops. 

Combinations, — Xanthamylamide is insoluble in water. 

It dissolves in cold oU ofvUriol, and water added to the solution sepa- 
rates oily drops. 

Iodine dissolves in cold xanthamylamide, forming a red solution, whiob 
when heated, is deoolorised| with separifttion of a colourless oil, '^Bromine 



118 AMTLENE : AMIDOOEN-MUCLBUS C>oAdH*. 

forms with xanthunylamide a wbite solid mass which yields a milkjr 
liquid with alcohol; and on adding water to this liquid, a colourless oil 

separates out. , . 

An alcoholic solution of xanthamylamide does not precipitate an 
alcoholic solution of acetate of lead or protochloride of copper. 

Mercury-compound. — Xanthamylamide and mercuric chloride, both 
dissolved in alcohol, form a copious precipitate consisting of white 
feathery crystaLs, which may be purified by washing with cold alcohol, 
and dissolving in a large quantity of boiling alcohol; the solution on 
cooling deposits the mercury- compound in the pure state. 

Dried in vacuo. Johnson. 

12 C 720 .... 10-46 10-60 

N 14-0 .... 2-03 1-48 

13 H 13-0 .... 1-89 2-06 

4Hg ....4000 .... 5809 6806 

4 CI 141-6 .... 20-56 

2S 32-0 .... 4-65 

SO 16-0 .... 2-32 



C»NH»SH)V4HgCl .... 688-6 .... 10000 

This compound is insoluble in water, but is gradually decomposed by 
prolonged contact with water, an odour of fusel-oil becoming perceptible. 
Gold oil of yitriol immediately decomposes it, with rise of temperature, 
blackening, and evolution of hydrochloric acid. — Nitric acid acts with 
energy upon it. — Gold hydrochloric acid has no effect upon it; but on 
boiling, a portion of the mercuric chloride is dissolved out, and another 
compound formed containing a smaller amount of the mercuric chloride : 
this latter compound is a soft, white solid substance, which adheres with 
tenacity to the sides of the vessels, and when heated, melts into a white > 
opaque oil. — Goncentrated ammonia, in the cold, immediately decom- 
poses the original mercury compound, with formation of black mercuric 
sulphide. — The compound boiled with potash forms a black precipitate 
and emits an odour of fusel-oil. Baryta likewise decomposes it at a 
boiling heat, an aromatic volatile compound being evolved, and mercuric 
sulphide remaining behind. — Sulphuretted hydrogen decomposes the 
compound, separating an oily liquid, which is doubtless xanthamylamide^ 
but obstinately retains the hydrochloric acid generated in the reaction. 

An alcoholic solution of xanthamylamide does not precipitate an 
alcoholic solution of nitrate of Bilvcr. 

An aqueous solution of bichloride of platinum forms with an alcoholic 
solution of xanthamylamide, a copious yellow precipitate having a faint 
peculiar odour, and slightly soluble in alcohol; the solution when evapo- 
rated, deposits a yellow crystalline compound, the mother-liquor quickly 
turning brown, and on evaporation, deposits an amorphous brown residue, 
with copious evolution of hydrochloric acid. An alcoholic solution of 
biochloride of platinum forms no precipitate with xanthamylamide, but 
the solution on eyaporation deposits a red crystalline compound. 



Zantbamylamide diasolyee readily in alcohofani ether. (Johnaon.) % 



IN08INIC ACID. lift 



Inosmic Acid. 

LiBBia. Ann, FAarm. 62, 817. 

Fyom ro^ Mq mutcle. — Occurs in many kindfl of mnBcnlar flesb* fLiebig.) The 
flesli of poultry yields O'll p.c. of inosate of baryta ; but the heart of me oz and the 
flesh of the ox, pigeon, ray and cod does not yield any. (Gregory, Aum. Pharm, 
64, 106); neither does haman flesh. (Schlossberger, Arm. Pharrh, 66, 80.) 

JPreparation. — Flesh-jaice is nentralised with baryta-water, and 
evaporated in a strong current of air at 60^ (because inosinic acid is 
decomposed at 100°), till all the creatine has separated out (z, 250, b); the 
mother-liquor then evaporated somewhat further; gradually mixed with 
small portions of alcohol till it becomes milky; then set aside for a few 
days; and the resulting white or yellow, granular, laminar or needle- 
shaped crystals (a mixture of inosate of baryta, and creatine, together 
with phosphate of lime, if only a small quantity of baryta-water has 
been added, or inosate of potash, if the baryta-water has been added in 
excess), collected on a filter, and washed with alcohol; and its solution in 
hot water mixed with chloride of barium,, whereupon it yields on cooling 
crystals of inosate of baryta, which are purified by recrystallisation. To 
obtain the free acid, either the solution of the baryta-salt is decomposed by 
the exact quantity of sulphuric acid required;— or the copper-salt is pre* 
pared by decomposing the baryta-salt with acetate of copper, then suspended 
in water, and decomposed by sulphuretted hydrogen; the filtrate, which 
exhibits a brown turbidity from the presence of sulphide of copper, deco- 
lorised with animal charcoal, and the filtrate evaporated to a syrup. 

Properties, — The syrup obtained by evaporation does not yield any 
crystals, even after standing for a week, but when covered with alcohol, 
it is converted into a powder. It has an agreeable taste like that of 
broth and reddens litmus strongly. 

DeeomposUians. —1. The syrupy acid, evaporated with nitric acid, 
yields a small quantity of colourless crystalline grains. — S. Heated with 
peroxide of lead and dilute sulphuric acid, it turns the peroxide white 
and forms a liquid, which, after removal of the sulphuric aeid, yields 
needles by eraporation. 

Combinatumi. -— Inosinic add dissolves readily in water, and is preci- 
pitated from the ooncentrated solution by alcohol iu white amorphous 
flakes. 

The Inatatea of the AUkalis, when heated on platinum-foil, give off a 
strong but pleasant odour, like that of roa«t meat. 

Inosate of Potash. — Obtained in part directly from the flesh-juice 
{vid, sup.), partly by eafeful precipitatiQn of the baryta-caU with earbonate 



120 AMYLENE: AMIDOGBN-NUCLBUS CUAdSHH)*. 

of potaflh. — Long, slender^ foar-sided prisms which give off 22*02 p.c. wator 
at 100^ and in the dry state contain 20*73 p. o. potash. They dissolve 
readily in water, but are insoluble in alcohol, and are precipitated by 
alcohol from the dilute aqueous solution, in the form of a white granular 
powder, but from the concentrated solution, in delicate nacreous laminio 
which thicken the liquid to a pulp. 

IwMOie of Soda. — Pine silky needles, very easily soluble in water, 
insoluble in alcohol. 

InosaU of Baryta. — The free acid does not precipitate baryta-water, 
but when the liquid is set aside and evaporated, laminsD of the salt are 
produced. {PreparatUmtpAl9), — Nacreous, elongated, four-sided laminoB, 
which after drying-look like polished silver. They give off 19 07 p.c. 
water ( = 7 [6] At.) at 100 . Dissolve in 400 pts. water at W, more 
readily in hot water, but less in water at 100° than at 70°. The solution 
saturated at 70° deposits part of the salt on boiling in the form of a 
resinous mass. If a quantity of the salt, which would dissolve in a 
certain quantity of water at 60° to 70°, is heated with the same quantity 
of water to the boiling point, a portion of the salt remains undissolved, 
and by continued boihng, even loses its solubility in water of a lower 
temperature. 



BaO 

IOC 


At 100^ 
60-0 


• •»• 

• •«• 
■ ••• 

• ••• 


31-71 ... 
24-83 ... 
11-59 ... 
207 .... 
29-89 ... 


Liebig. 

30-41 

24-63 


2N 


■ *•■««■■«■ ^O V 


11 '37 


5 H 


5-0 


•.... «*o& 


9 


72-0 


30*98 








C">N«H»BaO»« 

CWN«H»BaO».., 
6 HO 


241-6 

CryttaU. 

241-6 

54-0 


• ••• 

«•■• 

• >•» 


100-00 ... 

81-73 .... 
18-27 ... 


10000 

Liebig. 

.... 80-93 
19*07 









CM>N«H«BaO>« + 6Aq .... 295*6 .... 100-00 100*00 

Liebig gires for the salt dried at lOO"", the formula fiaO.C'N'H'O"*. 

With Ztm^-water, free inosinic acid behaves as with baryta-water. 
It giyes a white precipitate with Z^oc^salts. 

InotaJte of Copper. — The free acid and its soluble salts form with 
acetate of copper, a beautiful green-blue precipitate, which dries up to a 
light blue amorphous powder, and does not blacken when boiled with water, 
or dissolve, with the exception of a mere trace; it is insoluble in acetic 
acid, but dissolves with blue colour in ammonia. 

Inomte of Silver. — The alkaline inosates form with nitrate of silver 
a white gelatinous precipitate resembling alumina, which scarcely blackens 
on exposure to light, and dissolves to a small extent in pure water, less 
in silver-solution, and abundantly in nitric acid or ammonia. 100 pts. 
of the dry potash -salt form with silver-solution, a precipitate containing 
49'99 p. c. oxide of silver. 

JlooM dissolres oily tracofl of inosinic acid; dher none. (Liebig.) 



VALERONITRILE. 121 



Az(hnueleti8 C^NRK 

Valeronitrile. 

ScHLiEPER. (1846.) Ann. Fharm. 59^ 15. 

DuMAs^ Malaguti & Leblanc. Campt. rend, 25, 658. 

GucKELBQRGEB. Ann, Pharm. 64, 72. 

Cyanide qf Butyl f Cyanhydrate de Buiyrdne, 

Formation and Treparatum* 1. Dry valerate of ammonia or rale- 
ramide is distilled with anhydrous phosphoric acid, (Damas, &c.) 

NH»,CMH»CM - C^NH' + 4H0 
and: 

CWNH"0* - C»NH» + 2H0, 

Valeronitrile may also be prodaced, but not so readily, by passing 
valeramide through a red-hot tube filled with lime. (A. W. Hofmann, 
Ann. PTiarm, 65, 56.) 

2. When ^lue (Schlieper) or casein ^Gnokelberger) is distilled with chro- 
mate of potash and dilute sulphuric acid, valeronitrile passes over together 
with several other products. — 2 pts. of glue are left to swell up in 50 
pts. of water; 15 pts. of oil of vitriol added; and the mixture, after cooling, 
poured into a retort containing 8 pts. of bichromate of potash and dis- 
tilled, till, towards the end, the liquid, which becomes continually greener, 
no longer boils quietly, but begins to froth strongly. The distillate thus 
obtained, which is white and turbid, has an acid reaction, and smells 
strongly of hydrocyanic acid, is rectified over mercuric oxide, which 
decomposes the formic acid present, with evolution of gas, and retains 
the hydrocyanic acid, in the form of cyanide of mercury; And the liquid 
which first passes over, mixed with oily drops, is collected apart and 
several times fractionally rectified per se, till the oil which passes over is 
accompanied by 'only a small quantity of watery liquid, — then at a 
gentle heat over magnesia, to retain the benzoic acid, the receiver being 
changed as soon as, in place of a transparent, colourless oil and a clear 
watery liquid, a milky liquid gradually depositing oily drops, begins to 
pass over. The first oil is dehydrated by means of chloride of calcium, 
and slowly distilled with the thermometer; the receiver changed at 110°, 
because that which passes over at 90° is chiefly valeracetonitrile, while 
at 110^, the mixture of that body with valetronitile, and from 110° to 
140° principally the latter distils over; and this last distillate subjected 
to two more distillations, the portion which distils over between 1 22° and 
130° being collected apart in the former, and that which passes over 
between 124° and 127 in the latter: this last portion is pure valero- 
nitrile. . (Schlieper). — Or 1 pt. of casein is dissolved in a mixture of 
S pts. oil of vitriol and 6 pts. water contained in a retort; a solution of 
2 pts. bichromate of potash in 10 pts. water added (a larger quantity 
would produce yalerianio acid instead of raleronitrile); the reaction 



122 AMYLENE ! AZO-miCLEUS CU>NH'. 

which ensues moderated by the addition of 14 pts. more water (30 pts. 
in b1\); the distillate shaken up and redistilled with mercuric oxide; the 
distillate thus obtained neutralized with chalk, and redistilled; and 
the neutral distillate subjected to repeated fractional rectification, 
whereby there is obtained, first a milky distillate mixed with drops of 
colourless oil, and ultimately the latter only. When this distillate is 
further rectified, propylic aldide passes over below 120"*, and between 
120° and 140°, chiefly yaieronitrile, which may be purified by repeated 
rectification, the first and last portions that pajss oyer being set aside. 
(Guckelberger.) 

Properlies. Transparent, colourless, very thin liquid which refracts 
light strongly, sp. gr. 0*81 (Schlieper); 0*813 at 15\ (Guckelberger.) 
Boils at 125* (Schlieper); at 125° to 128°. (Guckelberger.) — Vapour- 
density = 2*892. (Guckelberger.) Smells like bitter almond oil and 
salicylous acid (Schlieper), and has an aromatic, burning, and bitter taste. 
(Guckelberger.) Makes a transient grease-spot upon paper. (Schlieper.) 



IOC, 

N. 

9H 







Schlieper. 


Guckelberger. 


60 


.... 72-29 .. 


.••..* 1X9A . 


....••. /l-oO 


14 


.... 16-87 ., 


16*95 . 


16-79 


9 


.... 10-84 .. 


10-60 . 


10-88 



C"NH» 83 .... 100-00 99-48 9958 

Vol. Density. 

C-Tap<>^r 10 4*1600 

N-gM 1 09706 

H-g«s 9 0'623 7 

Vapoar of Valeromtrile 2 5*7543 

1 2-8771 

Dfwmpodtum$. Yaieronitrile, when set on fire, bums with a white 

luminous flame, and without smoke. (Schlieper, Guckelberger.) 2. In 

sunshine, it is decomposed b^ chlorine or bromine, with formation of 
hydrochloric or hydrobromic acid. (Schlieper.) — 3. With oil of 
vitriol (also, according to Guckelberger, when distilled with dilute 
sulphuric acid), it is resolved into Bulphate of ammonia and free vale- 
rianic acid. (Schlieper.) 

CWNH» + 4H0 « NH» + C»«H«»0*. 

Nitric acid, hydrochloric acid, and ammonia have no action npon it. 
(Schlieper). — 4. With aqueous fixed alkalis, it is resolved with perfect 
tacility into a valerate of the alkali and free ammonia (Schlieper, Guck- 
elberger); — 5. It is decomposed at ordinary temperatures by potassium, 
into cyanide of potassium, hydrogen ga«, and a peculiar hydrocarbon! 
(Dnmaa, &o.) 

CwnXnnailcyM. Yaieronitrile dissolves with tolerable fiunlity in water 
(Schlieper) in about four times its volume of water. (Guckelberger.) 
It mixes in all proportions with akohol and cthtr. (Guckelberger.) 



AlfTL-URBA. 123 

Appendix to TalenmUriU. 

Valeracetonitrile. 

ScHLiEPEB. (1846.) Ann, Pharm. 59, 12. 

Prodaced in the preparation of valeronitrile from gelatin, in larger 
quantities tban the yaleronitrile itself, and passes over first in the rectifi- 
cation 9f the oil after dehydration by chloride of oalcium (p.l21), especially 
between 68° and 90°. The valeracetonitrile may be freed from admixed 
valeronitrile by rectifying it again^ and collecting only that which passes 
over np to 76 , and then once more, collecting only np to 71°. 

Transparent, colourless, strongly refracting, thin liquid, of sp. gr. 
0'79; boils between 68^ and 71°; leaves npon paper a grease-spot which 
quickly disappears^ smells like VBleronitrile but much more agreeably 
ethereaL 



26 C 

2 N 


156 .... 60*93 .. 

28 .... 10-94 .. 


Schlieper. 

61-35 

9*42 


9A U 


24 .... 9*38 ... 




6 


48 .... 18-75 . 


17-83 









C»N«IP«0" 256 .... 100-00 10000 

[The equation given by Schlieper for this formula, which does not quite agree with 
the analyiis, viz. : 

4C»HW0< + 3C<HH)* + 4NH» - 16HO «» 2C»N«H"0», 

is verj improbaUe.] 

DecampositioM. 1. Valeracetonitrile is easily set on fire, and bums 
with a faintly luminous flame. — 2. When chlorine gas is passed through 
it, a large quantity of hydrochloric acid is evolved, and the liquid becomes 
heated, and, if left in the cold, deposits white crystals of a chlorine- 
compound. — 3. With bromine, in a closed bottle occasionally opened, it 
gradually forms a bromine-compound which crystallizes in needles, and 
another which is liquid and has a terrible odour, attacking the nose 
and eyes. — 4. It is decomposed by oil of vitriol, yielding sulphate of 
ammonia, valerianic acid, and acetic acid. — 5. With aqueous fixed 
alkalis also, it is resolved^ even at ordinary temperatures, into valerate 
and acetate of the alkali, and free ammonia. — Nitric acid, h^drochlorio 
acid and ammonia do not exert any decomposing action upon it. 

ComhiHaU<m$. It dissolves in water much more copiously than 

ether. 

Mixes in all proportions with alcokol and' ether. (Schlieper.) 

Conjugated Compounds. 

Amyl-urea. 

C»N«IPH)» = C*(C»*NH»)Ad,0» = C"(C*NH*)AdH»,0». 
WuBTZ. (1851.) Compt. rend. 32, 417. 



124 AMTLENE: AZO-NUCLEUS C»NH». 

Prodaced ia small qnantitj in the deoomposition of alloplisnate 
[cjanurate] of amyl by ammonia. Decomposed by heated potashJej into 
amylamine and carbonate of potash. Forms with nitric acid, crystals 
which are permanent in the air. (Wnrtz.) 

Wortz has likewise obtained on ethamylurea = C^*N*H'^^ 



f Valeryl-urea, 

C"N*H"0* = (?(C»NHW0»)Ad,0« =5 Ci«((?NH*0*)AdH^,0». 

N. ZiNiN. J. pr. Chem. 62, Z55i N, Arm. Chm. FAys. 44^ 57. 
F. MoLDENHAUER. Ann Fharm. 94, 100. 

Obtained by the action of chloride of valeryl on nrea. (Zinin, 
Moldenhaner.) The action requires the aid of heat^ being scarcely 
perceptible at ordinary temperatures. (Zinin.) 

The compound resembles acetyl-nrea (ix, 292), but is less soluble. 
(Zinin.) Deposited from the hot aqueous solution in microscopic laminn 
having a pearly lustre, and soft and unctuous to the touch. The alco- 
holic solution yields slender needles, which under the microscope, appear 
like transparent four-sided prisms. Melts at 191", and when carefully 
heated in a tube, yields a crystalline sublimate of broad iridescent lamin». 
It is nearly insoluble in cold water and alcohoL (Moldenhaner.) 

Moldenhanei'. 
12 C 72 .... 60-00 49-^ 

2 N 28 .... 19-45 

12 H 12 .... 8-33 8-79 

4 O 32 ... 22-22 

CiON<H»0> 144 .... 100-00 ^ 

May be ngarded as CPN^CHSCioH'O^jOS. 

It was not found practicable, by acting upon tbis compound with chloride of yaleryl 
to replace a second atom of hydrogen in urea by valeryl. (Moldenhaur.) f . 

IT Amylopiperidine. 

C»NH" = C"H",C"NH" = C»<>NH»<»(C"H") 
Cahours. N. Ann. Chim. Phya. %%, 79; Chem. Soo. Qu. J. 6, 181. 

Obtained hj the action of iodide of amyl on piperidine. (x, 448.) 
Scarcely anpr action takes place at ordinary temperatures; but the mixture 
soon solidihes when heated in sealed tubes placed in the water-bath; and 
if, after the action has gone on for some days, the crystals are dissolved 
in a small quantity of water, and the liouid distilled in contact with 
fn^ments of caustic potash, amylopiperidine passes over in the form of 
a limpid liquid, the odour of which is both ammoniacal and amylic. After 
drying over fused potash, it is colourless and boUs at 186 . Vapour- 
density = 5 •477. 



20 C 


STIBAMYLS. 
....... 120 .... 77*41 


Cahonrg. 
77'54 


N 

91 H 


14 .... 13-55 

21 .... 9 04 


13-64 

9-17 








C»NH» 

C-Taponr .. 

N-g«8 

H.gM 


155 .... 10000 

Vol, 
20 


100*35 

Density. 
9*3200 




0-9706 


21 


1*4553 








2 

r 1 


11*7459 
5*8729 



}25 



Amylopiperidine is less soluble in water than the ooiresponding 
methyl and ethjl-compoands. (x, 450, 451.) 

The HydriodaU C^NH'^^HI forms lar^j^e white shining lamioo. 

PUainumrwU.-^ C»NH« HCl,PtCI» — When bichloride of platinum 
is ponred into a hot aqueous solution of amylopiperidine, dark, orange- 
oolonred oily drops are deposited, which solidify in a few hours, pre- 
senting a crystalline aspect. On dissolving this product in dilute alcohol 
and eyaporating slowly, the platinum^salt separates in very hard prisms, 
often of considerable size and of a fine orange colour, eren when the 
quantity of material operated upon is yery small. (Cahours.) ^. 



Appendix to the Amylene-series 

1. Cacodyl of Valerianic Acid. 

When valerate of potash is distilled with an equal weight of arsenious 
acid, a heavy, oily, slightly yellow liquid passes over, which has a 
penetrating, disagreeable, aJliacious odour, fumes strongly in the air; 
but does not take fire spontaneously. With corrosive sublimate it forms 
a thick white precipitate, the alliaceous odour disappearing at the same 
time, and being replaced by an aromatic odour something like that of 
valerate of amyl. The oily liquid is soluble in water, and appears to 
reduce oxide of mercury. When kept for some time in an imperfectly 
closed vessel, it is entirely converted into a mass of large, hard, shining, 
four-sided prisms, which are nearly colourless, and after pressure between 
paper, inodorous: they have an acid reaction, dissolve in water, and are 
completely decomposed by oxide of silver, (W. Gibbs, Sill. Am, J. 
[2], 15, 118; Ann. Pharm. 86, 222.) 



2. Stibamyls. 

F. Bbrlb. J. pr, Chem, S5, 385; Ann. Pharm. 97; 316; Ckem. Soe. 
Qu. J, 9, 282. 

These compounds are formed by the action * of iodide of amyl on 
antimonide of potassium. The latter substance (prepared by Lowig's 



126 8T1BAMTLS, 

process, ix, 79) is finely pnlrerised, with addition of about half its balk of 
dry sand; then introdnced into glass flasks, in such Gmantity as to fill them 
to aboat two-thirds, and iodide of amyl added sufficient to moisten the 
mass thronghoQt. After some time, and generally not till after the 
application of heat, a violent action takes place, attended with volatili- 
sation of the excess of iodide of amyl, which may be condensed by 
surmounting the flask with a distillation-tube- The flasks are then 
corked, their contents (a grey, pulverulent, coherent mass,) softened when 
cold with a small quantity of water, and emptied into a capacious 
cylinder, previously filled with carbonic acid gas. In this vessel, the 
product is repeatedly exhausted with ether; the ethereal solution, after 
it has become clear by standing, poured into a large fiask filled with car- 
bonic acid, and completely distilled ofi* after addition of water or ether. 
The residue consists of stihtriamyl^ protected from the action of the air 
by the water which is still present. 

If the stibtriamyl, prepared as above, is contaminated with free 
amylio alcohol (as when the iodide of amyl used in the preparation is 
impure) or with iodide of amyl, the following method may be adopted 
for the preparation of pure compounds. The impure stibtriamyl is 
dissolved in a mixture of ether and alcohol; bromine in alcoholic solution 
carefully added till its colour just begins to be permanent; then the 
bromide of stibtriamyl precipitated by addition of a large quantity of 
water; the bromide converted into oxide of stibtriamyl, by means of 
silver-oxide suspended in alcohol; the resulting solution again precipitated 
by water; the separated oxide dissolved in hydrochloric acid and alcohol; 
the pure chloride precipitated by another addition of water, and freed 
from a small quantity of water by continued heating at 1 00°^ and the 
use of chloride of calcium. 

Pure gtihtriamyl is a transparent, slightly yellowish liquid, very viscid 
below 20^, more mobile at higher temperatures. Has a peculiar aromatic 
odour, and a bitter, somewhat metallic and very persistent taste. Sp. gr. 
= 1*1333 at 17^. In contact with the air, it fumes strongly, but does 
not take fire; it decomposes at the same time, with separation of a white 
powder. A drop of it placed on a piece of bibulous paper, and exposed 
to the air, becomes so strongly heated that the paper-fibre is charred. In 
presence of very small quantities (2 per cent.) of amylic alcohol or iodide 
of amyl, stibtriamyl is also decomposed on exposure to the air, but 
without fuming or sensible rise of temperature. It is insoluble in water; 
sparingly soluble in absolute alcohol; very easily soluble in ether. 
Heated for eight daj's with iodide of amyl in a sealed glass tube placed 
in the water-bath, it does not show any inclination to combine. — 
[According to Cramer (Pharm. Cenir. 1855, 465)> stibtriamyl is a transparent, tolerablj 
mobile liquid, having a disagreeable alliaoeoua odour which excites coughing. Its 
sp. gr. is r0587. It is insoluble in water; bat dissolves readilj in alcohol and ether. 
It fumes in the air without taking fire, and forms (by evaporation of the ethereal 
solution ?) a transparent bitter, varnish-like mass which ultimately solidifies.] 





Smtriamyl 
... 180 .... 52'63 .... 

... OO .... VOd .... 

.... 129 ..... 37-72 




Berl^. 




30 C 

33 H 

Sb 


.... 53*55 .... 52*56 .... 
.... 10-00 .... 10-00 .... 


51-66 
1000 


{C«>H")»Sb 


... 342 .... 10000 









STIBTBIAMTL. 127 

Stibtriamyl oombines with oxygen, iodine, ftc.| forming oomponnds, 
in which Berl6 sapposes 1 At. of the radical to be united with 2 At of 
oxygen, &c.; the same yiew, in fiftct, as that proposed by Lowig for the 

compounds of stibethyl (ix, 80). — For another new of the constitntion of the 
compoiiDds of metaUiodal radicali, containing 1 At. metal to 3 At. of an alcohol* 
radical, tee z, 523. 

Oxide of Stibtriamyl is produced by slow eyaporation of an ethereal 
solution of stibtriamyl in contact with the air. There then remains a 
ffreyish-yellow, yery viscid, resinous mass, which becomes somewhat more 
luid when heated, but readily decomposes at a higher temperature. 
Tastes and smells like stibtriamyl. Insoluble in water; sparingly solnble 
in hydrated alcohol and in ether; easily soluble in absolute alcohol. The 
alcoholic solution precipitates the oxides of the heavy metals from their 
salts. It dissolves readily in acids, and the resulting compounds are 
precipitated from their alcoholic solutions by water. 

Chloride of Stibtriamyl, — ^As obtained by dissolving the oxide in hydro- 
chloric acid, or by the method already described (p. 126), it is a yellowish, 
translucent liquid, viscid at ordinary, comparatively mobile at higher 
temperatures, heavier than water; dissolves in alcohol and ether. When 
precipitated from the alcoholic solution by water, it obstinately retains 
small portions of water and alcohol, from which it can only be freed by 
continued heating to 100^, and drying over chloride of calcium. Has a 
peculiar smell and taste, like the radical. Decomposes above 160^. 

Berl^. 

8b 120 .... 81*23 

80 C 180 .... 43*69 44*59 .... 43*63 

33 U 33 .... 8*09 8*2 «« 9*00 

2 CI 70 .... 16-99 116'83 

(C»H")»Sb,CP.... 412 .... 100*00 

Iodide of Stibtriamyl is obtained by dissolving the oxide in hydriodio 
acid and precipitating by water, or by adding iodine to the nuiical as 
long as it is decolorisea. Very much like the chloride. Bromide of 
Stibtriamyl is prepared in like manner, and exhibits similar properties. 



fik 


129 


.... 

.... 


21*65 
30-20 .. 
5-54 .. 
42-61 .. 


Berl^. 


30 C 


180 


••*».. m\f mO 


33 H 


99 


6-10 


2 1 


126 


4000 








(C»H")«Sb,P 
8b 


468 

Bromide. 
129 


.... 

.... 
.... 
.... 


100*00 

85*70 
35*86 .. 
6*57 .. 
31-87 .. 


Betl^. 


30 C 


180 


36-04 


33 H 


33 


6-75 


2 Br 


160 


32-28 









(C»«H"y8b,Br» 502 .... lOO'OO 

When chloride or iodide of stibtriamyl is mixed with an alcoholio 
solution of nitrate of silyer, as long as a precipitate forms, and then 



128 STIBAMYLS. 

filtered, the filtrate forms an ' emulsion from which, after standing for 
some time in a warm place, two liquids separate; the upper being light, 
yellow and mobile, and the lower a deep brown-red oil. The upper 
layer, when slowly evaporated, yields slender white crystals grouped in 
stars; they may be purified by recrystallisation from dilute alcohol. The 
dark red oil likewise dissolves on addition of a large quantity of hydrated 
alcohol, and the solution, after standing for some time, yields the same 
crystals. These crystals melt at about 20 ; the fused mass does not 
dissolve in alcohol so readily as the crystals. This salt, the only crys- 
tal lisable compound of stibtriamyl, is the N Urate of Sihtriamyly 
(C**H")»Sb,2N0S (nitric acid by analysis 23*39 per cent; by calculation 
22*30); it is insoluble in water and ether, but dissolves in hydrated alcohol. 
Haa a peculiar metallic taste. 

By decomposing equivalent quantities of sulphate of silver and a 
haloid compound of stibtriamyl, dissolved in alcohol, Sidphats of StUh 
triamyl is obtained in solution. This salt was obtained only as an oily 
body, which yielded 18-03 per cent, sulphuric acid; the formula 
(C"H")2Sb,2SO* requires 18-26 per cent. 

The white powder, formed by the action of the air upon stibtriamyl^ 
is insoluble in ether, alcohol, and water; it does not dissolve in hydro- 
chloric acid, but imperfectly in fuming nitric acid; slowly in aqua-re^ia. 
It remains unaltered even when strongly heated, not decomposing below 
a red heat. Berl6 supposes it to be (C"H")'Sb,2S0* + 2SbO». When 
sulphuretted hydrogen was passed for some time through this compound 
suspended in alcohol, a white powder immediately separated, which 
gradually assumed an orange colour, and then formed a pulpy mass, which 
could not be filtered. After addition of a large quantity of alcohol and 
ether, the liquid, when left to stand in a warm place, deposited an orange- 
red, flocculent precipitate, which, after drying, formed a brownish-yellow 
powder, insoluble in alcohol, ether, and water; this powder decomposed 
at a very high temperature, and took fire when fuming nitric acid was 
poured upon it. Berl^ regards this compound as (C^<'H^^)'SbS' -h 2SbS' 
(it gave 18*38 per cent, sulphur, the formula requiring 17'59^. A com- 
pound, supposed to be identical with this, is formed by passing sulphu- 
retted hydrogen for some time through an alcoholic solution of oxide of 
stibtriamyl. 

Stihbiamyl. — When the product of the action of iodide of amyl upon 
iodide of potassium, instead of being exhausted with ether, was distilled 
in an atmosphere of carbonic acid, a liquid passed over, which was freed 
from nndecomposed iodide of amyl by distillation over antimonide of 
potassium. The liquid thus obtained gave off when heated to 80°, a 
colourless gas, which had a peculiar odour; burnt with a bright flame 
diffusing a white smoke of antimonic oxide; was not absorbed by water; 
but when left for some time in contact with it, deposited a white coating 
of antimony on the sides of the vessel. After the gas had been driven 
off, the liquid was greenish yellow, had a peculiar aromatic odour and 
bitter taste; was tolerablj mobile, and heavier than water. It was inso- 
luble in water, but miscible in all proportions with alcohol and ether. 
Exposed to the air, it does not fume or become heated; when set on fire 
it bums with a very bright flame, diffusing a white fume of antimonic 
oxide; when heatea in pure oxygen gas, it explodes with the greatest 
violence; fuming nitric acid decomposes it with considerable evolution of 
heat. This compound is StibhiamyL 



STAMNAMYLS. 129 

Bcrl^. 

Sb 129 .... 47-6 

20 C 120 .... 44-3 4513 .... 4330 .... 44«3 

22 H 22 .... 8-1 8-80 .... 9-01 .... 8'60 

(CWH")>8b .... 271 .... 1000 

When an ethereal solution of stibbiamjl is lefl to evaporate in the 
air, the resulting oxide absorbs carbonic acid. The radical heated for 
some time to 100^ in a stream of dry earbonio acid, yielded a liquid 
similar in properties to the pure radical, but more viscid. This liquid gave 
42 10 per cent, carbon, and is regarded bjr Berll as (C"H")*SbO,CO», 
this formula requiring 41*52 per cent. C. The haloid salts of stibbiamyl 
are gummy liquids; the sulphate and nitrate are precipitated from their 
alcoholic solutions by water in the form of gummy masses, which dry 
up to amorphous solids. 

[According to Werther {J.pr. Chetn. 64, 505), the product obtained by the actioii 
of iodide of aroyl on antimonide of potassinm in an atmosphere of carbonic add, cannot 
be distilled without deoompoaition : but by extracting the mats with ether, a solation 
is obtained^ which, when left to evaporate in the air, appears to form the oxides of two 
radicals, one soluble and the other insoluble in ether ; both yield crystallisable salts.] 



Zinc-amyl. C»oH"Zn. 

Franklamd. Ann. Pharm. 85, 360; Chem^ Soc. Qu. J. 6, 64. 

Produced by the action of zinc on iodide of amy I at 180^. 

[CWH»I + 2Zn = Znl + CWH"Zn.] 

It is a colourless transparent liquid, which fumes in the air, but does not 
take fire. By water it is resolved into oxido of zinc and hydride 
of amyl. 

CWH»Zn + HO «=. ZnO + C^H^.H. 



3. Stannamyls. 

A. GftiMH. /. pr, Chem, Ixii. 385; Ann. Phaiin, 92, 883. 

Formatton and Preparation. By the action of iodide of amyl oil 
stannide of sodium. — Iodide of amyl acts with violence on an alloy of 
1 pt. sodium and 6 pts. tin (ix, 92), especially if the iodide contains 
amylic alcohol, and the stannide of sodium is not mixed with sand. 
About 2|^ or 3 oz. of stannide of sodium is quickly pounded in an iron 
mortar with twice its weight of sand; the mixture immediately intro- 
duced into a glass flask of 5 or 6 times its bulk, and sufficient iodide of 
amyl added to form a pasty mass ; a distillation-tube then adapted to the 
flasK; and the mixture left to stand for some minutes. If no action takes 
place at ordinary temperatures, the flask must be heated in the water- 
oath, but removed as soon as the materials begin to act; the action then 

VOL, XI. K 



130 STAKKAMYL?* 

^068 ou rapidly and with so muoh evolution of heat, that tlie ezeess of 
iodide of amjl distils over completely. The flask is then to be closed 
while still hot, and the same process is pursued with several other flasks. 
The dry, yellow, pulverulent mass, which remains in the flasks after 
cooling, is then introduced into a bottle filled with ether and shaken up 
strongly several times, and the whole left to stand, without closing the 
vessel ai r-tight, till the ether separates quite clear. The ethereal solution is 
then decanted and the residue repeatedly treated with ether, as long as 
that liquid extracts any thing from it. The ethereal solution thus formed 
contains the following radicals : JStannamyl, C^°H"Sn; Bistannampl 
C»*>H"Sn«; Methylme-stannximyl (C^°H'^)»Sn»j MdhstanTuimyl (C»°H")^n^ 
Methstannhiamyl (C'^H^^/Sn^ These compounds may be separate by 
either of the following methods : 

A. The ethereal solution is mixed with alcohol and the ether distilled 
off; the alcoholic solution when cold, decanted from the matter which 
has separated out, then saturated with iodine, and the iodide of IfetJutann- 
hiamyl extracted with ether; the whole of the radical of this compound 
remains in the alcoholic solution. The mass which separates out 
is next dissolved in ether; the ethereal solution saturated with iodine; 
the ether distilled off; and the residue dissolved in absolute alcohol. The 
alcoholic solution is now poured, with agitation, into potash-ley, which 
must not be in too great excess, whereupon a white unctuous mass is 
precipitated, consisting of a mixture of the oxides of bistannamyl, methy- 
lene-stannamyl and stannamyl^ while the oxide of mdhstannamyl remains 
for the most part dissolved in the alcohol. The precipitate, after sepa- 
ration from the liquid, is treated with ether, which dissolves the oxides of 
histannamyl and methstannamyl, leaving undissolved the oxides of Hann- 
amyl and meOiylene-stannamyl. This insoluble residue is treated at a 
moderate heat with alcohol and a little sulphuric acid, whereupon the 
sulphate of stannamyl remains undissolved, while the sulphate of methy- 
lene- itannamyl passes into the alcoholic solution, and may be precipitated 
therefrom by water in the form of a tough mass which subsequently 
hardens. Or, the oxides may be treated with alcohol and hydrochloric 
acid, and the resulting solution left to evaporate : the chloride of mdhy- 
lene-stannamyl then crystallises out first. Lastly, the ethereal solution is 
distilled to expel the ether, and the residue treated with cold alcohol, 
which dissolves the oxide of methstannamyl and leaves undissolved the 
oxide of bistannamyL 

B. The ethereal solution, which contains the whole of the radicals 
and has been mixed with a little alcohol, is left to evaporate slowly in 
the air. The radicals then gradually oxidise, and the oxides of sUinn- 
amyl and methylene-stamiamyl separate out, while the rest remain in 
solution. The liquid is then diluted, and the residue again treated with 
alcohol, whereby the oxides of methstannamyl and methstannhiamyl are 
dissolved, while the oxide of Listannamyl remains for the most part 
undissolved. On saturating this alcoholic solution with hydrochloric 
acid and adding water drop by drop, the chloride of methstannamyl 
separates in a state of purity, while the chloride of metfistannbiamyl 
dissolves with tolerable facility, even in hydrated alcohol. 

Properties, The stannamyls in the free state are unctuous, non- 
volatile bodies which do not possess any very characteristic odour. They 
are insoluble in water, but dissolves readily in ether. In alcohol they 
dissolve for the most part less readily in propoHion as they contain more 



STANNAMTLS, 



131 



tin. They are bat little altered by exposure to the air, neither fuming 
nor taking fire. Faming nitric acid oxidises them with great violence, 
generally causing strong detonation and proiection of the mass, but 
without setting it on fire. — When the ethereal solution is left to evapo- 
rate in the air, the radicals quickly oxidise. — Bromine added drop by 
drop to the radicals, causes a violent reaction and considerable evolution 
of heat; this effect also takes place on the addition of bromine or iodine 
in alcoholic solution. — The oxides of all the stannamyls are separated 
from their salts by ammonia. Their solutions have a strong alkaline 
reaction. All the compounds of the stannamyls are non- volatile, and 
most of them inodorous. They exhibit for the most part, bat little 
tendency to crystallise. 

Bjbtannamyl. C"H"Sn'. — The o»ide is a perfectly transparent mass, 
having the consistence of turpentine, and brittle in the cold. It dissolves 
very sparingly in absolute alcohol, readily in ether and in a mixture of 
ether and alcohol. 

The chloride is also a viscid, transparent mass, soluble in alcohol 
and ether. So likewise the sidphate. 



2 Sn 118 .... 50-89 

C^H" 71 .... 36-04 

O 8 .... 4-07 

C»0H"Sn»,O 197 .... lOO'OO 

Chloride. 

2 Sn 118-0 .... 52-56 

CMIPi 71-0 .... 31-63 

a 35-4 .... 15-81 

C"H"Sn«,Cl .... 224-4 .., 10000 



.•••*•.. 



Grimm. 
58-92 



Grimm. 



15*48 



StANNAMYL.— C^H"Sn. [Likewise obtained by Frftnkland. (Chem. 8oe. 
Qif. /. 6, 62).] The oxide is a dazzling white, amorphous, inodorous 
powder, nearly insoluble in ether, somewhat soluble in boiling alcohol. 
Gave by analysis 40 15 and 42*53 p. c. tin, the formula C'<^H"SnO 
requiring 42*75. 

The chloride is, above 15% a thick transparent oil, but solidifies into 
a crystalline mass between 4° and 5^ Tt has a faint odour, like that of 
camphor, is unctuous to the touch, and bums with a bright^ green-edged 
flame. Dissolves readily in alcohol and ether. 



Chhride, 

Sn 59-0 

IOC 600 

11 H 11-0 

CI 35-4 

CWH"SnCi 165-4 



Grimm. 

35*65 34*20 

36-25 37-79 

6-65 6-72 

21*45 20*26 

100*00 98-97 



Stdphate, G^H"SaO,SO*. — White amorphous powder insoluble in 
water and ether, sparingly soluble in alcohol. Gave by analysis 21*90 
and 21-98 p. c. S0% the formula requiring 2 2 47 p. c. 

K 2 



13 J BTAKNAMTLS. 

MsTHTLBiTE-dTAKNAMYt. (C**H*')*Sn*. — The oxide resembles that of 
stannamjl. Gave 4887 and 44*10 and in another preparation^ 43*82 
p. c. tin, while the formnlA (C"H")"Sn*,0 requires 4403 p. c. 

Chloride. — Separates from the alcoholic solution in distinct prismatic 
crystals, which melt at 70° into an oily liquid, and solidify again in a 
crystalline mass on cooling. Smells somewhat stronger than the chloride 
of stannamyL Less soluble in alcohol. 

Grimm {mean), 

2 Sn 1180 .... 89-93 ^. 39*33 

20 C 1200 .... 40*60 39*63 

22 H 22-0 .... 7*45 7*70 

CI 35*4 .... 12*02 11*53 

(C»H")*8ii«,Cl .... 295*4 .... 100*00 98*19 

iSWt>Aa^.— (C^®H^^)*Sn*0,SO'. — Remains as an amorphous mass, 
when the alcoholic solution is evaporated. Dissolves readily in alcohol, 
and is separated from the solution by water in the form of a white 
flocculent powder, which at 100° cakes together in a resinous mass. 
Analysis gave 13*14 p. o. sulphuric acid, the formula requiring 12*99 p. c. 

Mbthstannamtl. (C^°H")*Sn*. — The oxide is obtained by shaking up 
the ethereal solution of the chloride with a snmll quantity of alcoholic 
potash-solution, then adding a large quantity of water, and leaving the 
ethereal solution of the oxide which then separates, to evaporate. 

The chloride is a faintly yellow transparent oil, which is insoluble in 
water, readily soluble in alcohol, and may be precipitated therefrom 
by water. 

Oxide, Grimm. 

2Sn 118 .... 34*80 35*43 

80 C 180 .... 5309 52*36 

S3H 33 .... 9*74 951 

O 8 .... 2-37 2*70 



(C»»H»)^n«0... 389 .... 10000 ... 

Chloride. 
30C 1800 .... 48'83 ... 


100*00 

Grimm* 

32*30 

47*31 


33 H S3-0 .... 9'31 ... 

CI 35*4 .... 9*67 ... 


10-36 

9*24 



JCWH")»Sn»a.... 866*4 ....100*00 99*21 

SnlphaJte. p«H*^)'SnH),S(H. — Obtained by adding sulphuric acid 
to the alcoholic solution of the oxide; then precipitating by water; 
washing the precipitate with water; redissolving it in alcohol; and 
leaving the solution to evaporate. The salt then remains in the form of 
a transpannt amorphous mass, whidi dissolved pretty easily both in 
aloohol and ether. Contains 10*82 p. e. sulphuric add (calcnlation* 
10 85). 



r 



STANNAMYLS. 133 

Methstannbiamtl. (C**H")*Sn*. — Colourless oily liquid readily 
soluble in alcohol and ether. 

Oxide. — Colourless, mobile oil easily soluble in alcohol, and having a 
pleasant odour like that of jasmine. 

Grinii|i« 

.... 28-78 29-33 .... 29-21 

... 58-54 58-05 .... 57-05 

... 10-73 10-64 .... 10-01 

... 1-95 1-98 .... 3-73 



2 Sn 


118 


40 C 


240 


44 H 


44 


O 


9 



(CWH»ySn»,0 .... 410 .... 10000 100-00 .... lOO'OO 

Chloride. (C"H")*Sn»,CL— Colourless oil, soluble in alcohol even if 
hyd rated, but precipitated from the solution on addition of a larger 
quantity of water. Ghiive by analysis 8*33 and 8*20 p. o. chlorine (ealou- 
lation, 8*11 p. c.) 

Iodide, — Crystallises at low temperatures, but melts ei^ily into aq 
oily liquid. (Grimm.) 

Grimiii. 

2 Sn 118 .... 22-84 22-27 

40 C 240 .... 46-46 

44 H 44 .... 8-33 

I 126 .... 23-87 23^68 

(C«>H"/SnM 528 .... 100-00 

HrpRARGAHYL. — Iodide of amyl exposed to sunshine in contaqt 
witb metallic mercury, yields a compound similar to iodide of hy4rargo- 
methyl. (Prankland, Ann. Pharm. 85, 204.) IT. 



134 BENZENE: PRIMARY NUCLEUS C»H«. 



COMPOUNDS CONTAINING 12 AT. CARBON. 



Benzene Seeies C^'H*. 



Benzene. C»H«. 

Faraday. PkU. Trans, 1825, 440; also Sckw. 47, 340 and 441; also 

Fogg. 5, 306. 
MmcHBBLicH. Bei'l. Ak. d, W. 1834; abstr. Fogg. 29, 231; also Ann. 

Fharm, 9, 39. 
Peligot. Ann. Chim. Fhys. 5Q, 59. 
Mansfield. Chem. Soe. Qu. J. 1, 244; alaoiitn. FAarm. 69, 162. 

Bicarhuret fff ffydroffen (Faraday) ; Benzin (Mitscherlich) ; Benzon (Liebig) ; 
Benzol, Phine (Laurent) ; Fune, (6m.) 

Formation. 1. When benzoic acid is heated with excess of lime 
(Mitscherlich), or when its Tapour is passed over red-hot iron. (D*Arcet, 
Ann. Chim. Fhys. 66, 99.) — 2. By the dry distillation of kinic acid. 
(Wohler.) — 3. By heating phthalic acid with lime. (Marignao, Ann, 
Fharm. 42, 217.)— 4. Bypassing bergamot-oil over red-hot lime. (Ohme, 
Ann. Fharm. 31, 318.) — 5. By passing fats through red-hot tubes. 
(Faraday.) — 6. By the dry distillation of coal. (Uofmann, Mansfield.) 
A good process for finding benzol in such products of distillation, is 
given by Hofmann. {Ann. Fharm. 55, 201.) 

Freparation. 1. A mixture of 1 pt. benzoic acid and 3 pts. pf 
slaked lime is distilled at a gently increasing heat; and the oily benzol 
which has passed over is separated from the water, and rectified after 
being shaken up with a little potash. 3 pts. of benzoic acid yield 
1 pt. of benzene. (Mitscherlich.) 

2. The benzene obtained in the preparation of bntylene (x, 6C), still 
retains a certain quantity of the oil C^H^; to free it from this impurity, 
it must be melted; then, after solidification at — 18°, repeatedly pressed 
upon paper with a glass rod, so as to make the oil soak into the paper; then 
melted again, and poured out into cakes in moulds of tin-foil: these pressed 
in a hydraulic press between several layers of filtering paper which has 
been dried by heat and left to cool; and finally deprivea of all moisture 
by distillation over lime. (Faraday.) 

3. From Coal-tar. The tnr which passes over in the distillation of 
illuminating gas from coal, contains, according to Mansfield and others, 
variable quantities of the following substances : sulphuretted hydrogen; 
ammonia; hydrocyanic acid; acetic acid; an oil which boils between 60"^ and 
70°, and becomes brown and resinous by oxidation; benzene; carbolic acid; 
aniline; picoline; pyrrol; an oil having the composition C^'H^; toluene 



BENZENE. 135 

C**H'; cumene C"H"; leucol; naphthalin C*H* (in small qnantitj, 
approaching to ^, according to the nature of the coal and the manner 
in which the process is conducted): cymene C^H^*; chrysene^ and 
anthracene. 

The tar is black, viscid, and of specific gravity 1-12 to 1*15. When 
it is distilled on the manafacturing scale in large iron vessels, ammoniacal 
gas passes over first, then Water containing ammoniacal products, and a 
yellow or brown mobile oil, of sp. gr. 0*900 to 0*950, and having a 
disagreeable odour proceeding from ammonia, picoline, &o. : this thin oil, 
the quantity of which continually increases in proportion to that of the 
water, is called lig?U oily crude naphtha or light naphtha, (It is purified 
in the manufactories by rectification, a portion of heavy naphtha 
{vid. in/,) still remaining in it; then by agitating the rectificate, — which 
is colourless at first, but has an ofiTensive odour, and gradually turns 
brown from formation of resin, — with oil of vitriol, which thereby acquires 
a dark red colour; and again rectifying the coloured naphtha decanted 
therefrom. It is then colourless, free from naphthalin, and has no longer 
any unpleasant odour.) 

By again distilling the coal-tar with a fresh receiver, a yellow 
stinkmg oil is obtained called dead oil or heavy naphtha, which sinks in 
water, yields more or less crystallised naphthalin, and contains leucol and 
anthracene, besides oily hydrocarbons boiling between 200° and 800% 
and aniline. (It serves for common lamps and torches, for preserving 
wood used in building, and for the preparation of lamp-black.) 

The residue which remains after the distillation of the heavy 
naphtha, and solidifies on cooling into a black mass called Fitch (nsed 
for the preparation of asphalt, and when dissolved in a small quantity of 
heavy naphtha, serving as a black iron- varnish), gives off, when still 
more strongly heated, first a buttery mass consisting chiefly of anthra- 
cene; then a yellowish more resinous distillate; and finally, when the 
iron retort becomes, heated to redness, an orange-yellow, inodorous 
powder, which feels glutinous between the fingers. In the retort there 
remains a very hard coke difficult to burn. 

When the still impure light naphtha is distilled, its boiling point 
rises, beginning at 100 and ultimately attaining 200"" to 220°. The la«t 
distillate generally yields crystals of naphthalin; the residual black 
brown mass, different from pitch, and consisting chiefly of oils resinised 
by oxidation, yields, when more strongly heated, a distillate containing, 
besides a little water, a red oil having a very peculiar odour, but little or 
no anthracene. 

When the light naphtha is several times alternately shaken up with 
dilute sulphuric acid, washed with water, agitated with dilute potash; 
washed with water, agitated with sulphuric acid, &c, &o, till it is freed 
from all basic and acid impurities, it appears but little diminished; but 
has lost the greater part of its disagreeable odour; and no longer colours 
clean fir-wood yellow (as when it contained aniline), or firwood moistened 
with hydrochloric acid purple (from containing pyrrhol); and no longer 
destroys the cuticle. When thus purified, it begins to boil at about 100° 
about f of it distilling over at 150°, and the greater part of the 
remaining ^ at 200°, the portion which distils over near 200 , sinking in 
water and solidifying as it cools. If in this distillation, the receiver be 
changed at every 5°, and each of the resulting distillates rectified b^ 
itself, also with change of receiver at every 5° (during which process, it 
is found that a distillate obtained at a certain temperaturej e.y, at 110^ 



136 BENZENE: PRIMARY NUCLEUS C»U<. 

to IIS"^, begins to boil ni a lower temperature, e,g. at 90", aad rises aboai 
Q(f or 40*^ higher, e.g. to 120°); and if all the rectificatea obtained at the 
same temperature are mixed together and again rectified, and the process 
continued in the same manner, till the whole has been ten times sub- 
jected to fractional distillation, the residues of which distillations are 
brown, especially at the beginning, — the boiling points exhibit distinct 
intervals, and there are obtained (after removal of the less volatile distil- 
lates which crystallise in consequence of containing naphthalin) five oils of 
differept degrees of volatility, and smelling like rook-oil but yet differ- 
ently one from tbe other, and of sp. gr. from 0*86 to 0*88; vis. 

A. Oil boiling between 60° and 70°, smelling like garlic and sulphide 
of carbon, very small in quantity. It combines for the most part with 
qH of vitriol, and on addition of water, a solid aromatic substance sepa- 
rates. Perhaps a mixture of benzene, which crystallises out from it 
below — 20°, and two more volatile oils. 

£. Oil boiling from 80° to 85°, amounting to -f^ of the light 
naphtha : Benzene. 

C, Oil boiling from 110° to 115°; in large quantity. May be set on 
fire, even when cold, by contsct with a flame; imparts to air passed 
through it at ordinary temperatures the property of burning with a blue 
flame. Consists chiefly of toluene C^^H^ 

2>. Oil boiling from 140° to 145°. In large quantity. Behaves like 
Gumene. Air passed through tbe cold oil is not rendered inflammable. 

JS, Oil boiling from 170° to 17 /i°. Forms but a small portion of 
the light naphtha (but a large portion of the heavy naphtha.) It has 
a density of 0*857 and consists of cymol C^H'^ (Mansfieldj see also 
Bitthausen, J. pr, Ohem. 61, 74), 

a. To obtain merely the benzene, it is suflicient to repeat the above- 
described rectification ^ve instead of ten times. The portion which 
distils over between 80° and 90° is left to crystallise at — 1 2°; thrown 
in a finely divided but closely pressed state on a strong cloth strainer 
irbich is fixed in a cylinder cooled to — 22°; and the air partially 
exhausted below the strainer by working a piston, so as to force the oil 
through it by atmospheric pressure : a Beart's cofiTee-machine is very well 
adapted to the purpose. The still impure benzene which remains on the 
filter in the form of a snowy crystalline mass, is left to thaw gradually 
(the last portion generally melts at + 4° to + 5°); the remaining liquid, 
which becomes continually poorer in foreign oils, collected in several 
bottles placed one after another below the funnel; and each of these 
fractions left to freeze by itself, and again fractionally thawed till the 
whole melts at + 4° to -h 5°. (Mansfield.) 

b. The portion of the light naphtha which passes over first in the 
distillation of the coal-tar, and therefore contains a smaller portion of 
the more fixed oils, is distilled from a metal still, and the vapours passed, 
first upwards into a chamber surrounded with water, (or into a worm 
tube), in which the oils that boil above 100° condense and run back, and 
then downwards into the cooling apparatus; and the resulting distillate 
rectified in the same manner, only that the temperature of the sur- 
rounding water is not allowed to rise above 80% and the distillation 
stopped as soon as the heat in the retort begins to rise above 00°. This 
rectificate, only half of which solidifies at — 20°, is shaken up with 
one-fourth of its bulk of oil of vitriol (or better, first with tV of its bulk 
of stronff nitric acid, and then, after decantation therefrom, with ^ of oil 
of vitriol), and rectified (without separatiop from the oil of vitriol) till tbe 



BENZBNB. 137 

bqiliiig pqint ia the retort rises to 80". If this rectificate, on being 
piixed with oil of Titriol^ aiBsumes a colour darker than straw-^jellow^ it 
Diuat be again distilled with oil of yitriol, then washed with water and 
afterwards with an alkaline ley. The oil of Titriol frees the liquid from 
alkaloids^ and oxidises the oil which turns brown and boils at 60'' to 70% 
but without acting on the benzene, even when heated. The nitric acid 
likewise purifies the liquid by oxidation : it is trne that it produces a 
certain quantity of nitrobenxene, but this is left behind in the distil- 
lation. Lastly, the benzene is purified, as in the preceding process, by 
freezing, pressure, &c. (Mansfield.) 

Properties. Crystalline in the cold, of sp. gr. 0'956; at — 18° it is 
nearly as hard as lump-sugar, brittle, and pulverulent; colourless and trans- 
parent; does not conduct electricity. (Faraday.) After slow solidification, 
it forms laminsB united in fern-like tufts : after rapid cooling, it resembles 
camphor or white crystalline wax. (Mansfield.) Melts at 5' 5° (at 7°, 
according to Mitscherlich), expanding at the same time by tv of its bulk 
(Faraday), and solidifies again at 0° (Mitcherlicb, Mansfield); in narrow 
vessels, however, it may be cooled considerably below 0° without solidi- 
fying, and then solidifies suddenly on being shaken or poured out. 
(Mansfield.) In the melted state, it is a thin oil; the bubbles which 
form on its surface when shaken quickly disappear : it refracts light 
strongly. (Mansfield.) Sp. gr. 0*85 at 15*5° (Faraday, Mitscherlich, 
Mansfield), 0-8991 at 0°. (Kopp.) — Boils at 80*4° under a pressure of. 
0-76 met. (Kopp, Pogg. 72, 223); between 80° and 81° (Mansfield); at 
about 82° (Peligot); at 855° (Faraday); at 86° (Mitscherlich); 80:8° 
(Church, Phil. Mag. J. [4], 9, 256), and volatilises undecomposed. 
Vapour-density = 2*752 (Faraday), 2770 (Mitscherlich, Mansfield.) — 
Smells like the illuminating gas produced from fatty substances, and 
somewhat like bitter almonds. (Faraday.) Its vapour does not produce 
narcotic effects when inhaled. (Snow.) 

Mitscher- Dumas & Nichol- 

Faraday. lich. Peligot. D*Arcet. Stas. Kopp. Bon. 

12 C ... 72 .... 92-31 .... 91-72 .... 91-62 .... 92-87 .... 9207 .... 922 .... 91-92 .... 92-3 
6 H .... 6 .... 7-69 .... 8-30 .... 7-76 .... 7*73 .... 7*93 .... 7*7 .... 7'76 .... 7-7 

C»H«.. 78 ....100-00 ....100-02 ....100-38 ....100-60 ....lQO-00 .... 999 .... 9968 ....1000 

Vol. Deniity. 

C-vapour 12 4-9920 

H-gaa 6 0-4158 

Vapour of Benzeue 2 5*4078 

1 2-7039 

DeeompasUioni. 1. The rapour passed through a red-hot tube is con- 
verted, with gradual deposition of charcoal, into a gaseous hydrocarbon. 
(Faraday.) The oil is very inflammable and bums with a bright, very 
smoky flame. (Faraday.) Solid benzene bums when set on fire, without 
previous fusion. (Mansfield.) Benzene volatilising in oxygen gas at 
ordinary temperatures, forms a mixture which explodes violently when 
an electric spark is passed through it 2 vol. ben zone- vapour consume in 
this manner 15 vol. oxygen-gas, 12 voL of which with 12 vol. carbon- 
vapour form 12 voL carbonic acid gas, and the remaining 8 voL with 



138 B£NZ£NB : PaiiatY NUCLEUS C^'H*. 

6 to], hydrogen form water. (Faraday.) Air charged with benzene- 
vapour, buriiB from a jet with a white smoky flame or with a violet flamei 
according to the width of the jet and the velocity of the stream; 
hydrogen gas charged with benzene vapour bums in a similar manner 
with a bright white flame. (Mansfield.) — 3. Benzene immersed in 
chlarme^as and exposed to the sun^ is converted, with rise of temperature 
and formation of hydrochloric acid, into crystals and an oil. (Faraday.) 
The oil consists of terchlorobenzene and the crystals of hydrochlorate 
of terchlorobenzene (Mitscherlicb); according to Peligot, this transfor- 
mation does not take place in the dark. — 5. Bromine dissolved in 
benzene likewise acts upon it only in sunshine, forming hydrobromate of 
terbromobenzeiie. (Mitschorlich.) Iodine does not act upon benzene 
even in sunshine. (Faraday.) — 6. Moderately strong nitt'ie acid has 
no action upon benzene even when distilled with it; but in the warm 
fuming acid, it dissolves, with evolution of heat, forming nitrobenzene, 
C^^XH', which partly separates in the form of an oil on cooling. 
(Mitscherlich.) Faraday observed reddening and an odour of hydro- 
cyanic acid. According to Abel, benzene is ultimately converted into 
nitrobenzene, by repeated distillation even with dilute nitric acid. — 
7. Cold anhydrous sulphuric acid converts benzene, with moderate rise of 
temperature and without evolution of sulphurous acid, into a viscid 
liquid, consisting of 5 to 6 per cent, of sulphibenzene C"H'SO', benzo- 
sulphuric acid, C^H*,2S0', and another acid, which forms a non-crystal- 
lisable salt with oxide of copper. With fuming oil of vitriol^ the same 
products are formed; the sulphibenzene however amounting to only 1 or 
2 per cent — Fonnation of sulphibenzene : 

C^H* + S0» « C»H»SO» + HO. 

Common oil of Titriol has no action upon it. (Mitscherlich.) — The following 
substances have no action upon benzene : iodine in sunshine ; potassium and aqueous 
alkalis at the boiling point of benzene (Faraday) ; non-fuming oil of yitriol even at the 
boiling point of benzene (Mitscherlich, Mansfield) ; aqueous chromic acid (Abel) ; 
phosgene-gas in sunshine (Mitscherlich) ; pentachloride of phosphorus. (Cahours.) 

Camhinalians. Benzene dissolves very sparingly in toater, imparting 
a strong cdoar to it. (Mitscherlich.) 

It dissolves small quantities of phospko^nu, nUphur, and iodine (the 
last with crimson colour : Faraday), more at a boiling heat, the excess 
separating on cooling. (Mansfield.) 

It dissolves bromine. (Mansfield.) 

It dissolves in toood-spirU. (Mansfield.) 

It dissolves very sparingly in alcohol, and is separated therefrom by 
water. (Faraday.) A mixture of 1 vol. benzene and 2 vol. alcohol of 
sp. gr. 0*85 gives a good light in lamps; but an addition of alcohol makes 
the flame duller, and an addition of benzene, more smoky. (Mansfield.) 

It dissolves very sparingly in etiier, (Faraday, Mitscherlich.) 

It dissolves readily in acetone, separating the water from that liquid 
if hydrated. (Mansfield.) 

It dissolves large quantities of oils both fixed and volatile, (Faraday, 
Mansfield), also camphor, wax, mastic, caoutchouc and gutta percha, 
small quantities of gumlac, copal, anime and gamboge, a tolerably large 
qnantity of quinine, small quantities of morphine and strychnine, but no 
oinchonine. (Mansfield) 



CARBOLIC ACID. 139 

Carbolic Acid. 

Reichenbaoh. Schw. 66,801 and 345; 67, 1 and 57; 68, 352. 

RuKGE. Po^^. 31,69; 32,308. 

Laurent. If. Ann, Ghim. Phys, 3, 195; also J, pr, Chem, 25, 401. 

Creosote (from xpea^, flesh and aw^ew, to preserve), Phenol, Hydrate 
of Phenyl, Hydrated oxide of Phenyl, Phenic acid, Phenous acid^ Spirol, 
Salicon [^N'efune']. — Reichenbacb, obtained, in 1832, from wood-tar hb 
creosote, and Runge in 1834, from coal-tar, his carbolic acid; Laarent also in 
1841 obtained from coal-tar, his hydrate of phenyl, and gave a correct ana* 
lysis of it. His investigations, as well as others of more recent date, showed 
that these three substances differ from one another only in their several 
degrees of parity. According to Gomp-Besanez {An7i. Pharm. 78,231, 
86,223; 96, 39) creosote (apparently that which is prepared from beech- 
tar) is essentially different from Laurent's phenic acid, inasmuch as it gives 
different results by analysis and totally different products with chlorine 
and nitric acid. But to establish this point, he should have examined 
creosote prepared by himself, not that procured from a manufactory. 
Volckel also (Ann, Pharm, 86, 66) regards creosote as different from 
hydrate of phenyl, but assigns to it a formula different from that given 
by Gomp-Besanez. Lastly from the experiments of Williamson and 
Fairlie {Chem, Soc, Qu. J. 7, 232), it appears that coal-tar creosote con* 
tains, besides hydrate of phenyl, the homologous substance G^^H'O' which 
may be separated by fractional distillation. 

Sources. In castoreum (Wohler), and in cows*, horses*; and human 
urine. (Stadeler, Ann. Pharm. 67, 360; 77, 17.) 

Formation. By the dry distillation of wood ^Reichenbach), of coal 
(Reichenbach, Runge, Laurent), of bones (Reichenoach), of gum benzoin 
(B. Kopp), of the resin of Xantatrhoea hastUis (Stenhouse), of salicylic 
acid (when rapidly heated), of alkaline salicylates and of saliretin 
(Gerhardt), of salicin with lime (Stenhouse), of kinio acid (Wohler), of 
chromate of polosin. (Bodeker.) 

Preparation. 1 . From BeechrUH>od Vinegar. — Thi« sabstance contains 
from 1 to 14 per cent, of creoftote, which rises to the surface as an oil, when the liquid 
is saturated with common salt or sulphate of soda. — The liquid is saturated by 

agitation with effloresced Glauber's salt at 70*' to 80 , at which tempera* 
ture it dissolves the largest quantity of that salt; the brown oil, 
amounting to 5 per cent, which rises to the surface, and consists of 
creosote, acetic acid, a small quantity of eupione and other oils, removed 
before it sinks to the bottom and mixes with the crystals of Glauber's 
salt; separated, after standing for several days in a cool place, from the 
acetic acid which rises to the surface, by removing the latter, and from 
the crystallising Glauber's salt by straining through linen; and then 
shaken up warm with carbonate of potash to free it from the remaining 
acetic acid. The oil which has been decanted from the alkaline liquid 
containing acetate of potash, and has become thicker, is distilled 



140 BENZBNE: PRIBIARY NUCLEUS C»H<. 

with water from iron retorts, care being taken to avoid percussive ebul- 
lition and not to burn the copious brown residue; the pale yellow oil 
which has passed over and' assumes a deep brown colour on exposure to 
the air, briskly agitated with very dilute phosphoric acid to extract the 
ammonia; the acid liquid then removed; the oil shaken up with fresh 
phosphoric acid; freed from the acid by repeated washing with water, — 
then again briskly agitated with an equal weight of warm dilute phos- 
phoric acid; and distilled with this acid, the watery part of the distillate 
being repeatedly poured back, till but little more creosote passes over, 
and the oily residue is thrown about in the water in thickish lumps. 
(There still remain small quantities of acetate and phosphate of potash 
and ammonia.) The colourless oil which has passed over is further 
dissolved, after decantation of the watery distillate, in cold potash-ley of 
sp. gr. 1'12, the layer of eupione which rises to the surface when the liquid, 
milky at first, is left at rest, being removed, and freed from the remaining 
creosote by repeatedly washing it with a weaker solution till the eupione 
has become tastless; the whole of the solutions containing an impure 
Compound of creosote and potash united; the mixture gradually heated 
to the boiling point in an open vessel, during which an admixed 
oil rapidly absorbs oxygen and becomes resinised; the mixture, which has 
become black-brown, treated, after cooling, with a sufficient quantity of 
sulphuric acid to set free all the creosote, which then exhibits a brown 
colour; and this creosote decanted while hot from the sulphate of potash, 
and distilled in a capacious glass retort, the distillation, however, not 
being continued to dryness or till the brown resinous residue begins to 
char: on this account the bottom of the retort should be surrounded with 
sand. The water contained in the creosote to the amount of 10 per 
cent, produces violent percussion during this process. This treatment 
with potash and sulphuric acid, and the distillation, are repeated from 
twice to four times, till the potash-solution, when heated in the air, no 
longer turns, brown, but only slightly reddish. The creosote separated 
from this solution by sulphuric acid, is well washed with water and recti- 
fied, and potash-lev dissolved in it in just sufficient quantity to redden 
turmeric peroeptibly, in order to keep back the remainder of any acid 
that may be present; the liquid then distilled over alcohol, as long as 
the creosote passes over without colour, at which stage of the process the 
residue amounts to about 4 or 5 times the volume of the potash-ley used; 
and the distillate, which should not turn brown even after several days* 
exposure to the air, several times rectified over alcohol, the anhydrous 
creosote which passes over after the percussive ebullition has ceased, and 
the heat has been raised, being collected apart, and a little oil left in the 
retort to prevent browning and burning, and the consequent necessity of 
repeating the entire process from the beginning. (Reichenbach.) 

2. From Beech-tar, — Thi« subsunce contoin«, betidei 20 tp 25 percent, of 
creosote : water, ammonia, hydrocyanic acid, acetic acid, eupione, an oil which turns 
brown and becomes resinised by exposure to the air« picamar, kapnomor, brown mouUIy 
[and resinous] matters, paraffin, sebaclc acid and oleic acid. (Reichenbach.) — a. The 
oily portion of the tar is ^distilled ofif in iron retorts, at a heat not suffi- 
cient to produce either tumefaction or charring, leaving 40 per cent, of 
pitch, which should have such a consistence that it is brittle in the cold 
but plastic at the beat of the hand. The acid watery layer, amounting 
to 15 p. c. of the two, is then decanted from the heavy oil which hns 
passed over, and if above this watery layer there floats a light oil chiefly 
consisting of eupionCi this is also removed. The lower oil is then 



CARBOLtC ACID; l4l 

distilled at a gradually increasing heat, the oil whicb first passes over 
being set aside as long as it floats upon water; the distillation stopped as 
soon as the appearance of heayy whitish-yellow vapours indicates the 
copious evolution of paraffin; and the whole of the oils thus obtained, 
separated by repeated distillation, with change of receiver, into an oil 
rich in eupione, which when redistilled to the end, yields a product 
that floats upon water, and an oil rich in creosote, which from the very 
beginning yields a product sinking in water. Carbonate of potash is 
then added to the latter, with heating and agitation, till it no longer 
causes effervescence, and a small sample of the oil shaken up with water 
lio longer reddens litmus; and the oil, after cooling at rest, is separated 
from the saline ley containing acetic acid, and rectified, setting aside the 
first portion of the distillate, in case it floats on water, and taking care 
not to bum the portions near the sides of the vessel: for this last reason 
the liquid should not be distilled to perfect dryness. The distillate is 
then repeatedly treated (as in the preparation from wood-vinegar) with 
phosphoric acid and water; distilled over phosphoric acid; dissolved in 
like manner in potash; the solution freed from the eupione which rises to 
the top, and heated in the air; the creosote separated by sulphuric acid 
and distilled; and the process repeated, from the treatment with potash 
Onward, just as in the preparation of creosote from wood-vinegar. — 
(p. 140; from the words t the colourless oil vibich has passed o^er is further dissolved, 
Sec. dowa to : and the consequent necessity of repeating the entire process from the 
beginning.) — In the distillation of creosote from coal-tar or animal tar, the 
treatment with carbonate of potash may be dispensed with; but the 
separation of the ammonia by phosphoric acid requires greater care. 
(Reichenbach.) 

b. Tar obtained from hard wood is distilled in a copper still of treble 
capacity, the portion which first passes over being rejected, and the dia« 
tillate not collected till a very acid liquid passes over, from which water 
throws down an oil, and the fire removed as soon as the liquid in the 
retort begins to decrepitate. The distillate is neutralised with carbonate 
of potash and distilled with a large quantity of water; the oil which 
first passes over and floats on water removed; and the distillation conti- 
nued, the water which passes over being repeatedly poured back into the 
still till the quantity of the heavy oil no longer undergoes any consider- 
able increase. This heavy oil is dissolved in potash-ley of sp. gr. 1*12; 
the eupione which rises to the surface taken ofi*; the alkaline liquid, 
wJiich contains an equal quantity of eupione in solution, distilled with its 
own volume of water, which must be renewed from time to time, as long 
as any eupione passes over; a quantity of dilute sulphuric acid equal to \ of 
that which is required to neutralise the potash, then introduced into the 
still; and the distillation continued, whereupon creosote containing eupione 
is first obtained, and then a small quantity of pure creosote; lastly, the 
contents of the still are slightly supersaturated with sulphuric acid; and) 
by further distillation, changing the receiver and pouring back the water, 
till no more oil distils over, the greater part of the creosote free from 
eupione is obtained. This pure creosote, together with the creosote-water 
which passes over with it, is mixed in a still with just sufficient potash-* 
ley to ffive it a slight alkaline reaction, and rectified, the water being 
repeatedly poured back as before. Lastly, the ci*eosote, after being 
mechanically separated from the water, is distilled from a glass retort in 
the sand-bath, the receiver being chauged and the neck of the retort 
dried as soon as all the water has passed over. Should the creosote thus 



142 BENZENE : PRIMARY NUCLEUS d^H*. 

obtained turn red on exposure to the air, it must be redistilled in tbe 
same manner. (Ed. Simon, Pogg, 32, 119.) 

c. Wood*tar is distilled with a small quantity of sand, and the oil 
which sinks in water is collected apart. This oil is then mixed in a 
basin with twice its bulk of water, to which sulphuric acid has been added 
in sufficient quantity to make the oil float upon it; gradually heated to 
the boiling point; and kept in a state of ebullition for some minutes. The 
brown oil, after cooling, is separated from the colourless acid liquid below; 
rectified; again treated with the above-mentioned acid liquid, whereby it 
is again turned brown; once more rectified; the pale yellow rectificate 
dissolved in a quantity of potash-ley not sufficient to dissolve the whole 
of the creosote; the oil rich in eupione which floats on the top removed; 
the alkaline solution heated with the above-mentioned acid liquid; the 
coloured creosote which separates, removed, washed by agitation with 
water, and rectified after being mixed with sufficient potash to give it an 
alkaline reaction; the colourless oil mixed with a small quantity of potash- 
ley and set aside for some weeks in an open bottle placed in a cellar; 
and the liquid, which has then become brown, carefully rectified. By 
this method, a large quantity of potash is saved. (Hiibschmann; Ann, 
Pharm. 11, 40.^ 

IT. d. The neavy yellow oil distilled from wood-tar by Beichenbach's 
process (pp. 1 40, 141) is dissolved in potash-ley; heated to the boiling-point 
with dilute, sulphuric acid; the separated creosote distilled with water; 
and these operations repeated several times. To purify the creosote thus 
obtained from certain oils which cause it to turn yellow by keeping, it is 
dissolved in excess of strong solution of potash; the solution mixea with 
water, and the separated oil removed; the clear solution boiled for some 
time in a still, whereupon a colourless oil of nearly the same density as 
the water passes over with it; and the boiling continued till the milky 
water likewise containing creosote which passes over, becomes clear on 
addition of dilute potash. The dark yellow compound of creosote and 
potash remaining in the still is then mixed with dilute sulphuric acid in 
such quantity as to leave it slightly alkaline, and distilled, whereupon 
colourless creosote passes over with the water. The creosote thus 
obtained began to boil slightljr at 100^; and as the boiling point steadily 
rose, creosote distilled over with the water; between 200 and 208^, the 
thermometer rose but slowly, and colourless anhydrous creosote then 
passed over; above 208^ the distillate consisted of creosote having a faint 
yellow colour; and at 220°, a small quantity of brown-black suDstanoe, 
viscid while warm, solid in the cold, and still containing creosote, 
remained in the retort. On rectifying the creosote which had passed 
over between 200^ and 208"^, the greater part distilled between 200° and 
205% the smaller portion between 205° and 209"*; the last portion of the 
distillate had a yellowish colour, and in this distillation also there 
remained a small quantity of viscid matter which solidified on cooling. 
(Vblckel, Ann, Pharm, 86, ^^,) %, — A sample of crude creosote pre- 
pared from beech-tar by Reichenbach's process began to boil at 90°, the 
boiling point steadily rising, and by far the largest portion distilling 
over between 203*5 and 208°. On again rectifying this portion, setting 
it aside for a day with fused chloride of calcium and rectifying once 
more, the boiling point remained constant for some time at 203*5 and 
then slowly rose. (Qornp-Besanez, Ann. Pharm, 86, 223.) Gorup- 
Besanez is of opinion that creosote boiled for some time with strong 



CARBOLIC ACiD» 148 

potasli-lej, as in Volckcrs process of pnrifioation, undergoes a slow 
decomposition (see p. 146). % 

[Respectinff tlie preparation of creosote, see also Kriiger, Repert, AT, 273); 
fiachner {Repert. 49, 84) ; KOae {Ann. Pharm, 16, 63) ; Cozxi {ReperL 55, 69.) 

3. From Coal-tar. — a. Preparation of Runge^s Carbolic acid, — 
12 pts. of the oil obtained by distilling coal-tar with oxide of copper, 
are mixed with 2 pts. of lime and 50 pts. of water, and the mixture set 
aside for eight hoars and frequently shaken; the brown-yellow watery 
filtrate thence resulting, boiled down to one-fourth, whereby aniline, 
leucol and pyrrhol are driven out; the liquid filtered when cold; the 
impure carbolic acid precipitated from the filtrate by hydrochloric acid in 
the form of a brown oil; this oil washed with water, after the aqueous 
liquid has been decanted ofi*; then distilled with water till -|- of toe oil 
hns passed over (the brown-black pitchy residue contains rosolic and 
brunolic acids); the distillate, which is milky at first, but afterwards 
deposits clear oily drops, mixed with a quantity of water sufficient to 
dissolve the oil, and precipitated by subacetate of lead; and the curdy 
precipitate of carbolate of lead, after washing and thorough drying 
(which is most easily efiected after the addition of a small quantity of 
sulphuric or hydrochloric acid), subjected to dry distillation, whereupon it 
melts, and gives off carbolic acid (or water at first, if not thoroughly 
dry,) in the form of a yellow oil, which, by rectifying with a fresh 
rceiver, may be obtained colourless and free from water. — The easiest 
method of obtaining a pure product, is at once to distil the carbolic ncid 
contained in the above-mentioned milky distillate, first with water, then 
with 4 or 5 per cent, of hydrate of potash. (Runge.) — In the distillation 
of the lead-precipitate, neutral creosote passes over first, and then acid creosote, which, 
from partial decomposition by heat, contains acetic acid, kapnomor and other products, 
and is therefore not completely soluble in potash. (Reichenbach, Pogg, 31, 497.) 

h. Preparation of Hydrate of Phenyl, according to LaiarerU, — CoaU 
tar is distilled till anthracene begins to pass over; the resulting oil recti- 
fied, collecting apart the portion which distils over between 1 5^ and 200°; 
this portion mixed with saturated potash-ley and pulverised hydrate of 
potash, whereby it is immediately converted into a white crystalline 
magma; this substance dissolved in hot water; the oil which rises to the 
surface removed; the lower alkaline liquid neutralised with hydrochloric 
acid; the impure hydrate of phenyl, which rises to the surface as an oil, 
washed with a little water, digested over chloride of calcium, rectified 
several times, and gradually cooled to — 10° in a closed bottle; and the 
resulting crystals of pure hydrate of phenyl, freed from the remaining 
fiuid portion by inverting tne bottle over another, care being taken to 
exclude the air, which might give up water to the crystals. (Laurent ) 
-—The tedious fractional distillations involved in this process may be 
considerably abridged by introducing into the portions which boil between 
186° and 188°, a few crystals of pure hydrate of phenyl; a considerable 
portion of the liquid then solidifies after a while in colourless needles, 
which, when separated from the liquid, distil at 1 84° and yield a subli- 
mate of pure hydrate of phenyl. (Williamson <& Scrngham, Chem, JSoc.- 
Qu. J. 7, 237.) 

When less carefully prepared, creosote may contain : 1. Water, A 
few drops of the creosote heated in a test-tube a little above 100°, deposit 
a film of moisture. ^- 2. Ammonia, Water saturated with such creosote 



l44 BENZENE! PRtMAtlt NtCLEtJS C'^H*. 

does Dot remain clear %rhen mixed with neutral acetate of lead, bat forms 
a greasy precipitate soluble in alcohol. — 8. Acetic acid may be suspected 
when the creosote reddens litmus. — 4. Eupicne, The Bolutiou of such 
creosote in concentrated potash gives up the eupione on dilution with 
water, the eupione then rising to the top. — 5. Easily axidablc oil wkicl^ 
quickly turns brown. Creosote thus contaminated turns brown in a day on 
exposure to the air. Its solution in a treble quantity of strong potash 
turns brown instead of remaining colourless or assuming merely a faint 
red tint Its saturated aqueous solution forms with a drop of ferric 
sulphate, not a red-brown but a black-brown precipitate. — 6. Ficamar, 
Such creosote tastes bitter. A drop of it dissolved in alcohol contaiuing 
a small quantity of baryta-water forms a white precipitate. It may be 
purified by twice distilling it with water, till only a small quantity of oil 
passes over with the water. The picamar being less volatile remains 
behind. — Kapnomor, which deprives the creosote of its corrosive action 
(t/. pr, Ckem. 1, 18), and a principle of tremendous emetic power 
{Pogg, 29, 62), are also found in badly-prepared creosote. (Reichenbach.) 

Pure carbolic acid should impart to fir-wood, on addition of hydro- 
chloric acid, a pure blue colour; a green colour indicates the presence of 
anilinei a brownish colour that of pyrrhol. — It ought not to turn brown 
in the air, even after addition of ammonia; and it should produce with 
ferric sulphate, not a red but a pure lilac colour. (Rnnge.) 

Creosote adulterated with at least 40 per cent of alcohol, forms a 
turbid mixture when shaken up with six times its volume of almond-oil 
at 20° to Z{f; alcohol likewise diminishes its specific gravity. (Lepage, 
J. Chim. med, 23, 491.) 

Properties. Ph. (hydrate of phenyl) crystallises at ordinary tempera- 
tures in long colourless needles, belonging to the right prismatic system^ 
ep. gr. 1065 at 1S°; (1'0627 according to Scrugham); melts at 34"" to dd"*; 
boils at 187° to 188° (at 184° according to Scrugham); smells very much 
like creosote, attacks the skin like that substance, and does not redden litmus. 
(Laurent.) — Carb. (Runge's carbolic acid) is a colourless oil of sp. gr. 1 *062 
at 20°; refracts light strongly ; crystallises under certain circumstances 
[when more oompletelydried 1] in long needles which do not melt till heated 
above l^"*; boils at 197*5°; has an empyreumatic odour, like that of caato- 
reum, and a strong, burning, caustic taste. On the skin, it forms brown and 
white spoto, which turn red in a minute, and peel ofi* after a few days. 
Its aqueous solution causes pain when introduced into the eye or into 
wounds (in the latter case producing coagulation of albumin, but not 
stopping the blood); plants immersed in it quickly wither. Neutral. A 
deal-shaving moistened with its solution in 300 pts. water, and then with 
hydrochloric or nitric acid, acquires in half-an-hour a beautiful blue 
colour, which is not destroyed by chloride of lime. (Runge.)-— 
The piece of wood is soaked in aqueous carboDic add, dipped for a moment into dilate 
hydrochloric acid, and then exposed to the sun. (StliJeler.) Fir- wood, even when 
simply moistened with hydrochloric acid, often exhibits a blue, violet or green colour oA 
exposure to sunshine. (Wagner, /. pr. Chem. 52,451.) — Kr. (creosote) is a 

transparent, colourless oil, of sp. gr. 1*037 (1*040, according to Oorup- 
Besanez, which does not solidify at — 27° [on account of the presence of 
water?]; refracts light more strongly than sulphide of carbon. It has the 
consistence of almond-oil; forms at 20°, drops three times smaller than 
those of water; makes grease-spots on paper which disappear in a few 
hours; does not conduct electricity; expands from 100 to 11 6"^ vol, whea 



CARBOLIC ACiBi 14S 

heated from 20"^ to 203"*; boils at 203'' under a pressare of 0*72 inet.; 
distils anchaoged and without residue; volatilises completely in a few- 
days when exposed to the air on glass; has a repulsive penetrating odour, 
at a distance like castoreum, when close, something like smoked meat; 
its taste is extremely burning and caustic (with sweetish after-taste); it 
corrodes the tongue, and is perfectly neutral. Kr. smeared on the skin, 
and washed off after a minute, leaves a spot which looks as if it had 
been singed, but is neither inflamed nor painful, and after a few days 
becomes brittle, the cuticle scaling off. In the eye or in wounds, it 
instantly produces a violent burning pain. Plants are killed by it, and 
likewise small animals, with convulsions. (Reichenbach.) Even dogs are 
killed by a few drops of it in a quarter of an hour, with convulsions* 
(Wohler 8c Frerichs, Ann. Pharm. Q5, 344.) 

Laurent, Gerhardt, 

Hydrate qfPkenffl. from Coal»tar, fiwn SaiieyUe acid, 

12 C 72 .... 76-59 77-13 76-04 

6H 6 .... 6-38 6-64 6-58 

2 16 .... 17-03 16-23 1738 

^11 - ■ — !■ .11 I . I » I.I II .III ■■ 

C^HW 94 .... 100-00 100-00 10000 

CreO9oi0, 
Gorap'Bennez 
Ettling. (mean qf 8 mialyses.) Derille. VSlckeL 

C... 7v*72 .... 74-53 ...I 
n.... 7*ov .... Sot ...< 
O.... 16-48 .... 17-60 .... 

100-00 .... 100-00 .... 10000 .... 10000 .... 10000 .... 10000 .... 100-00 

In Reichenbach's creosote analysed by Ettling, Liebig (Ann. Fharm* 
6, 209) suggests with reason that there was still water present-— 
^. Oornp-Besanes deduced from his analyses above>qnoted the formula 
C^H^'O^ which requires 76-47 C and 7*84 H. Vblckel resarded the 
creosote analysed by Oorup as impure, and attempted to purify his own 
by boiling with dilute potash (see page 142). For the creosote thus 
purified he deduced from his analyses the formula CP^H^^O', which requires 
72-72 C and 7*07H. — On the otner hand, Gomp, in a subsequent memoir 
(Ann. Pharm, 96, 39), states that creosote is gradually decomposed by 
boiling with potash. By dissolving creosote in strong potash-ley, boiling 
the solution for 5 hours on 7 successive days, till the milky liquid which 
distilled became clear on addition of dilute-potash (p. 142), then distilling 
the residue with sulphuric acid, and rectifying, a colourless creosote was 
obtained having the sp. gr. 1-057 at 13% boiling between 202"^ and 210% 
and dissolving completely in dilute potash and in acetic acid (a character 
which Volckel considers as essential to pure creosote). It gave by analysis 
74*76 to 74*98 and 7*78 to 7*84 H, numbers corresponding pretty nearly 
with the formukk C^H'H)^, which requires 75*39 C and 7*85 H. On redis- 
solving this creosote in potash, boiling the solution for fiye hours on four 
successive days, and separating the creosote from the residue as before, 
the amount of carbon was found to be diminished, analysis giving 
73*53 p. c. C and 7*68 H; and by again boiling this creosote with potash 
and separating as before, a sniall quantity of distillate was obtained, 

VOL. XI, L 







^^ 




"-V 




75-21 


.... 72-30 .... 


72-54 


.... 


72-92 .... 


72-45 


7-92 


7-60 .... 


7-60 


.... 


816 .... 


710 


16-87 


.... 20-10 .... 


19-86 


.... 


18-92 .... 


20-45 



146 BENZfiNB : PRIMARY KtJCLBUS C»H«. 

which gare 78*48 and 78*78 p. o. C, and 7*72 and 7*71 p.e, H, numbers 
agreeing pretty hearlj with the formnla C^H^*'KH*^ which requires 74*08 C 
and 7*45 H. The quantity of creosote was diminished at each boiling with 
potash^ so that a pound was ultimatelT reduced to a few grammes; and 
moreover in each case the liquid which distilled over at a certain time 
from the commencement of the boiling, gradually acquired by exposure 
to the air a purple-violet colour, the produetion of which was accelerated 
by addition of potash; but after the boiling had been continued for a still 
longer time, the distillate remained colourless on expostire to the air^ even 
after addition of potash. These phenomena are regarded by Gornp as 
indicative of gradual decompositioui which he supposes to consist in the 
substitution of oxygen for hydrogen. The potash with which the creosote 
had been boiled, always gave off carbonic acid on addition of sulphuric 
acid. — Deville*8 analyses (quoted by Gerhardt, TraUS de Ghim, org. 8, 20^ 
are extracted from a paper published by that chemist in 1848; the thira 
6{ these analyses was nuide with creosote prepared by Reichenbach him- 
self; the other two with products preparea by Pelletier. The results of 
these analyses differ considerably n-om those of Ettling and Uorup, and 
do not agree very well with the formula subsequently given by Deville, 
viz. C^H^^O^; but they agree very nearly with those obtained by Volckel. 
— Williamson, from experiments made by Fairlie {Ghent, Soc. Qu. J. 
7, 232) concludes that creosote (from coal-tar) is mainly a mixture of 
hydrate of phenyl with the homologous substi^nce hydrate of cresyl 
C^^H'O*. Probably the samples of wood-tar creosote anaJysed by Gorup- 
Besaiiez and others were similarly constituted. At all events^ the formula 
Q26||i6Q4 given \yj (}orup is nearly intermediate between C"H'0* and 
C"HW. IT. 

The radical theory assumes the existence of a radical, Phenyl = 
C''H», and an oxide of phenyl C"H'0, the hydrate of which C'>H'0,HO, 
is carbolic acid. According to this yiew, carbolic acid should be regarded 
as an alcohol, whereas it rather exhibits the relations of an acid aldide; 
aod ifi that character it is represented by the above forn^ula C"H*,0', 
(first assumed by Laurent, Eev, scienttf. 14, 841), the basis of which is not 
C^'H^ but the actually existing compound CH^ 

Deeompontiom. 1. Kr. may be set onfre in a heated spoon or in a 
wi6k> and bums withbut residue; producing a white veiy smoky flame 
{Reid^enbach); a yellbw yery smoky flame (Range); a smoky flame 
(Laurent). -^ 2. Kr. does not become odloured by exposure to air and 
suhshinoi but assumes a reddish tint when exposed to the air after very 
long boiling or When mi±ed with aqueous potash or atnmonia (Reichen- 
bach); compare p. 149. — 8. Kr. passed very slowly by drops through a red* 
hat poredain tube^ is resolved into a combustible sas loaded with naph* 
ihalin vapour; into crystallised tiaphthalin, and hard, ilron-blaek, graphite^ 
likd, Mled Up laminae of dmrcoal^ whibh do not bum at a M heat; 
together with a small quantitjr of tasteless, greasy soot, containing a 
Bubstance which dissolves readily in aleoheL (Reichenbach^ txSip. 
Hofmann, Ann: Phamt: 55) 205.) 

4. Ph. is converted by ehhrine iuto hydirochlorio a^d bichloroearbolic 
acids) then into terchlorocarbolie acid; and by bromine, with great evolu- 
tion of heat, iuto hydrobromic and terbromocarbolic acids. (I^ureUt) : 

tiDMH«D« + 6C1 - C»H>ClKJ» + 3HCl]. 

Chhrine-fa$ absorbed by cold Kr. foma hydrochloric acid and a brown 



CARBOUO ACIDi 147 

resin; froid oreofote-waier chlorine gas throws down a red oil. When 
chlorine gas is passckl into creosote, the liquid beeotnes turbid, subse- 
qnentLj giring off hjdroehloric acid, and acquiring, first a brownish, 
then a red pur|>le colour; no definite product appears to be formed. 
(Gorup-Besanex.) Bnmine dropped into Kr. forms a rose-coloured 
mixture, with ris^ of temperature and a crackling hissing noise; from 
creosote- wat«r it throws down a jellow*red oil. Alcoholic (but not 
aqueous) wdin€ precipitates froib creosott^ water a dark-eoloured oiL 
(Reichenbacfa.) — Kr. is not perceptibly altered bj distillation with an 
equal weight of iodine. (Gujot, J. tdefic, phys, 5, 230.) 

5. Chioride qf lime converts Kr. into a resiiious bodji — 6. Ph. 
treated with chlorate bf potash and strong hydrochloric acid, the action 
being ultimatelj assisted hy heat, is oouTerted, first into a red-brown, 
crystalline pastj mixture of ohloranil, and a red) viscid, fetid resin, which 
may be extracted by cold alcohol, and when distilled, melts> fortns char- 
coal, yields a distillate containing a large Quantity of hydrochloric acid, 
and k red solidifying oil consisting of terolilorooarbolic acid, and is finally 
eonyerted into a light yellow crystalline mass of ehloraniL (A. W» 
Hofoiann, Ann, Fharm. 52> 57.) 

C><HH)> •«- loa -I- £0 1- (^HnW + 6Ha (Hoftiistiii)& 

Kr. Also yields ohloranil fLaurent^ Ccmpt rend. 19, 574). — % According 
to Gorup-Besanes {Ann, Fharm, 86, 837), the products of tiie action of 
hydrochloric acid and chlorate of potash upon creosote are fftxachhrxff" 
lone C«K)1«H«0S and in stnaller quantity, Fentachhrofylone C"C1'H'0*. % 
— 7. Nitric acid dropped into Ph. produces a rattling hissing noise, And 
at a boiling heat conyerts it into picric acid. (Laurent): 

C»HH)« + «N0» ^ C»(NO*)mH)« + 8HO. 

*Carb. forms, eyen with dilute nitric acid, a red-brown inizture, which| 
wheh the hitrie acid is in excess, deposits a black resin. (Kunge.) Kn 
treated with strong nitric acid becomes heated, gives off red fumes, with 
sufficient violence to cause spirting, And acquires a dark brown colour. 
(Reiehenbach.) — Laurent ((7oinpe. rend, 19, 574), by boiling Kr. with 
dilute nitric acid, obtained picric acid, oxalic acid, and a brown resin 
which, when subsequently treated with ammonia and nitric acid, was 
resolved into picric acid and two other nitro- acids, which formed yellow, 
laminsd and needles with ammonia. (Comp, Oomp-BesAnes, Ann. Pkarm, 232) 
^i— 8. Oil of vitriol dissolves Ph. with slight elevation of temperature 
and in all proportions^ yielditag a colourless mixture in which sulpho* 
carbolic acid is formed. (Laurent). -» A mixture of Carb. with 4 pt 
oil of vitdfiol is colourless, but assumes a rose-colour at the boiling heat; 
a mixture with \ pt. oil of yitriol is pale yellow and beeonies yelldwish 
red on boiling; with excess of oil of vitjriol> A pale yellow mixture ia 
formed, which, at a boiling heat, gives off sulphurous acid and becomes 
black-brown. (Runge.) Kr. forms with -^j^ pi. of common or of fuming 
oil of vitriol, a rose-coloured mixture, which, on exposure to the air, 
becomes milky from absorption of water, limpid credsote afterwards 
separating out. With a larger quantity of oil of yitriol, a purple-red 
mixture is produced; with a still larger auantity^ a black-red transparent 
mixture, which when boiled gives off sulphuric acid and becomes bhick 
abd o{>aque. Oil of yitriol, distilled with excess of Kr. is completely 

L 2 



148 , BENZENE: PRIMARY NUCLEUS C»=H«. 

decomposed, creosote disiilliDg over at first and afterwards sulpliur. 
When Kr. is distilled with excess of oil of ritriol, it is completely decom- 
posed, sul phurous acid being evolyed, and the mass frothing ap, blackening 
and solidifying into a carbonaceous mass. (Reichenbach.) — Anhydrous 
sulphuric acid decomposes Kr. immediately, with deposition of finely* 
divided charcoal. (A. Vogel, Junr. 7. pr. Chem, 23, 512.) — Kr. forms 
with oil of vitriol a pnrple-red mixture containing a compound which 
forms a baryta-salt, soluble, but quickly decomposing when the solution 
is evaporated. (Qomp-Besanez.) — A mixture of sulphuric and nitric 
acid acts violently on creosote, ionuing a yellowish-red solution, which, 
when largely diluted with water, yields a small quantity of whitish- 
yellow, amorphous, explosive substance. (Gorup-Besanez.) 

9. Ph. immersed in aqueous chf^omie acid immediately turns black. 
(Qerhardt) — Bichromate of potash added to creosote* water slowly 
throws down a brown resin. Aqueous manganic acid dropt into Kr. 
becomes brown, the creosote at tne same time turning red. A small 
quantity of creosote-water added to aqueous manganic acid throws down, 
a brown oxide; excess of creosote-water forms a yellow precipitate 
soluble with yellow colour in alcohol. Boiling aqueous moli/bdie add is 
converted into brown molybdic oxide, the creosote assuming a yellowish- 
red colour. (Reichenbach.) — 10. Ph. as well as Kr. dropt upon peroxide 
of lead causes evolution of heat and slight hissing, and on subsequent 
boiling with water, forms a substance containing protoxide of lead. 
(Laurent). — No decomposition takes place on boiling Kr. with peroxide 
of lead or peroxide of manganese. — Kr. quickly reduces gold from the 
dilute hydrochloric acid solution; silver is reduced by it from the solution 
of the nitrate or acetate, slowly in the cold, quickly on boiling. (Reich- 
enbach.) If, Kr. heated with nitrate of silver produces a silver speculum; 
when dropt upon recently-precipitated silver- oxide, it becomes heated so 
much as to take fire with explosion; when silver.oxide is gradually added 
to creosote, the liquid assumes a dark colour, silver is reduced, and oxalate 
of silver formed, together with several resinous compounds. Kr. like* 
wise reduces the salts of other noble metals. (Gorup-Besanez.^ IT. — With 
bichloride of platinum, it slowly assumes a yellow colour ana deposits a 
brown resin soluble in alcohol. (ReichenlMich.) — 11. Ph. boiled with 
mercuric oxide or nitrate, reduces the mercury to the metallic state. 
(Laurent.) — Kr. heated with mercuric oxide reduces it to the metallic 
state, itself becoming red, and afterwards brown and more viscid; if 
sufiicient oxide is present, the Kr. is converted on cooling into a brittle 
resin. (Reichenbach.) — 12. Creosote-water, added to solution of ferrous 
sulphate, gradually throws down a red- brown adhesive mixture of 
resinised creosote and ferrous sulphate. (Reichenbach.) 

Ph. may be distilled undecomposed with glacial phosphoric acid. (Laarent.) 
13. Ph. in contact with pentachloride of phosphorus, immediately 
evolves hydrochloric and cholorophosphoric acid and leaves chloride of 
phenyl in the form of a heavy oil : 

C»H«0» + PCl« - HCl + PCl«Oa + CJ«CIH». 

(Cahonrsy Compt. rend. 22, 486; Gerhardt & Laurent, Campt. rend. 
28, 173).— f. 2 At pentachloride of phosphorus and 5 At. hydrate of 
phenyl yield chloride of phenyl, and terbasio phosphate of phenyl, toge- 
ther with chlorophosphonc acid [oxychloride of phosphorus] and hydro « 
chloric acid. (Williamson andSorugham, Chem. Soc. Qu. J. 7, 238.) 



CARBOLIC ACID* 119 

[The simplest expression of the foregobg lesult is given by the 
equation ; 

6(C«H»,H,03) + 2FCI* «- 2CJWa + P(C«H*)H)9 + PC1«0» + 5HC1. 

The quantity of chloride of phenyl obtained is however much smaller 
than this equation would indicate, the principal product being the phos- 
phate of phenyl. (W.)l IT. 

14. Ph. as well as Garb, and Er., in contact with potassium, especially 
if heated, gradually gives off hydrogen gas and forms needles. (Laurent.) 
The product of the action is carbonate of potash; if too much heat is 
applied, inflammation and explosion take place. (Runge.) Kr. with 
potassium or sodium, gives off hydrogen, especially on application of 
neat, becoming viscid and turning brown on exposure to the air. 

T. Kr. dissolves in caustic potash, and the solution becomes brownish 
after standing for a few hours; by continued boiling with potash, the 
creosote appears to undergo a gradual change, resulting in a diminution 
of the amount of carbon, and apparently consisting in a gradual substi- 
tution of for H. When Kr. is fused with hydrate of potash or distilled 
with alcoholic solution of potash, a small quantity of an oily liquid is 
obtained, colourless at first, but afterwards turning yellow, of strong 
refracting power, specifically lighter than water, having a pleasant 
aromatic odour and burning taste, distilling over between 180° and 190*^, 
inflammable, insoluble in water, soluble in alcohol and in ether : this 
product appears to be identical with Reichenbach's kapnomor. Creosote 
mixed with lime becomes heated and assumes a blackish colour; on 
heating the mixture, a milky liquid passes over between 100° and 180°; 
between 180° and 190® the above-mentioned li^ht oil; and between 203° 
and 208°, an oil heavier than water, and diffenng from creosote in odour 
and in composition. (Gorup-Beeanez, ^nfi. PAarm. 86, 223.) According 
to Volckel on the contrary, {Ann. Pharm, 87, 306) pure anhydrous 
creosote does not become heated by contact with recently ignited lime; 
on heating the mixture to the boihng point of creosote, that substance 
distils over unaltered; and it is only when the temperature is raised 
considerably higher, that the creosote combined with the lime is decom- 
posed, a small quantity of a yellowish oil being ^ven off, and at last a 
combustible gas. The yellowish oil exhibited a boiling point rising from 
120° to above 200°: Volckel regards the least volatile portion of it as 
identical with kapnomor. ^. 



CombinationB, With Water. 

a. Moist Carbolic acid. — The crystals of carbonic acid deliquesce 
in the air to an oil by taking up a trace of water, which makes scarcely 
any difference in the result of their analysis. (Laurent.) As carbolic add 
which ia no longer crystallisable containa, according to Gerhardt {Ann, Pharm. 45, 25), 
74'5 p. c. C, 6*9 H, and 19*6 O, it appeara to contain 1 At. water to 3 or 4 At. crys- 
talline carbolic acid ; and it is this small quantity of water that seems to oonstitnte the 
chief difference between Reichenbach's creosote and Laurent's hydrate of phenyl. 
It is difficult to dehydrate the oil completely; a lump of chloride of 
calcium causes it to solidify immediately. (Gerhardt.) 

h, Hydrated CarboUo add, — By brisk agitation with not too large a 
quantity of water at 20°, there is formed^ below the aqueous carbolic acid; 



160 benzenb: pbimabt nucleus c«>h«. 

fbQ oily lajrer oontainioff 10 pt4. water tq 100 pto, Kr, This quantity 
of water increases with tlie heat at which the agitation is performed* 
(Reichenbach.) 

c. Aqueous Carbolic acid; Creosote-water, — 1 pt. of creosote dis- 
solves at 20"* in 80 pts. and at lOO"" in 22 pts. water, partiallj separating 
ont from the latter on cooling. rReichenhach.) Carb. dissolves in 31 

?t8. water at 20^. (Range.) The solution exhibits, even to the 
0,000th degree of dilutioui the burning and afterwards sweetish taste of 
creosote; and on addition of excess of sulphuric acid, the creosote 
separates out (Reichenbach.) 

Boiliug Kr. dissolves a large quantity of crystallised horacie adi^ 
which is deposited as a powder on cooling. (Reichenbach.) 

Cold Kr. takes up a small quantity of phosphorusy and becomes 
luminous; when warm, it dissolves a larger quantity, forming a deep 
yellow solution. (Reichenbach^ The solution forms a black precipitate 
with nitrate of silver. (A. vogel, Junr. J. pr. Chem, 19, 897.)—* 
Kr. dissolves on agitation in 30 pts. of hot aqueous phosphoric acid of 
sp. gr. ri35, and forms with another portion of the acid a solution 
of 1 pi acid in 30 Kr. Both solutions become turbid on cooling, with 
partial separation of the dissolved substance. (Reichenbach.) 

Sulphur dissolves sparingly in cold creosote, but in 2*6 pts. of boiling 
creosote, which, as it becomes more saturated, assumes a yellow, then a 
green, and ultimately a brown and red-brown colour, and on coolinff, first 
deposits melted sulphur and then becomes filled with crystals of sulphur. 
(Reichenbach.) The pale yellow solution of sulphur m boiline carbolic 
^id, which smells of sulphuretted hydrogen, forms on cooling a solid 
white crystalline mass. (Runge.) ^r. mixes in all proportions with 
sulphide of carbon, (Reichenbach.) — Kr. dissolves a small quantity of 
sulphide cf phosphorus, forming a yellowish fuming liquid, which shines 
brightly in the dark if expos^ to the air. (Bottger.) 

Boiling Kr. dissolves a small quantity of sdenitm^ which is almost 
aJl deposited on cooling. (Reichenbach.) 

Oo|d Kr. dissolves a large Quantity of iodine, forming a brown-red 
liquidj whicl^ is not decomposed by boiling. (Reichenbach.) Similarly', 
Range wd I^iafvnt. Cold (sreosote shaken up with aquequs hydriodie acid 
dissolves a large quantity of it (Reichenbach.) 

^r. is not more soluble in aqueous hj/drochloria acid than in w^ter. 
(Reichepbaob.) 

Carbolateb. Obtained by combining the a^id with the pure bases ^not 
with the carbonatea) The carbolates of the aJkalis have an alkaJine 
reaction. The salts crystallise partially. A chip of firwood moistened 
with a solution of one of these salts and then dried, gradually turns blue 
when mojstened witli weak hydrochloric or nitric acid. (Runge.) 

Carholate of Ammonia, — Carbolic acid absorbs ammoniacal m 
abundantly pni with evolution of heat, forming carbolate of ammonia. 
(Laurent] Hoffman, Ann. Fharm, 47, 75.) This salt passed in the state 
of vapour through a glass tube at a low red heat, deposits a small 

Jiuantity of charcoal, but does not form any aniline, which, however is 
ormed at 300° in sealed tubes, and sparingly when an alcoholic solution 
of carbolate of ammonia is set aside for a month. (Laurent) Strong 
ammonia dissolves quickly in cold creosote, and the mixture tarns red when 
^exposed to the air. (Reichenbach.) The salt obtained with Carb. 
remains eelourles8,.and; even wh^n itjcontains but little an^moma^ejdubitB 



'^H lUkaline feafttion, exhales ammonia, and Yolatilisea. (jftpnge.) ^ir. 
4i69olv08 ia aiumonia, even in the cold] and the solution giyes o^ all its 
^^nmonia at ] 0Q°. (Gorup-Besanes.) 

Carbo,kUe of Jpakuk. — I. Carh. heated with a suffipient qm^ntitj qf 
pqtaseiom, g\ye^ off hydrogen and ie almost wholly (spn verted into a 
crystalline inass of carbolate of potash; wi^h a (Bmf|>ller qviantity qf 
potassium^ it forms an oil, ffhich deposits needles of the same s^lt on 
oooUiig. (lounge, Laurent.) — 2. The liquid formed by heating carb. 
with hydrate of potash solidifies in the oold to a pulpy mass qI qeedles. 
(Rnpge, Laurent) Kr. in contact with [excess of ?] hydn^te of potash 
becomes heated and forms an upper oily layer of creosote-potash, and 
below it, an aqueous solution of potash <x>qtaining a small quantity of 
creosote-potash in solution. In both layers there are formed nacrequs 
iamine of creosote-potash, which rise§ to iho surface as an oil when the 
liquid is heated, the laminsa reappearing as it cools. When the Kr. and the 
hydrate of pptash are l^ right proportion, the entire oily layer crys- 
tallises, and nnmeroiis crystals float even in the watery laver. In potashr 
ley of sp. g^. 1 3^. Kr. dissolves with evolutipn of hoat, without 
eeparation of an oily layer or of crystals. (Beicheohach.) Colourless needles 
(Laurent, Bunge), which, according to their mode of preparation (1), 
piust be C^'H^KO*. (Laurent.) Their eolution does not exhibit the 
corrosive aotioii of free carbolic acid. (Bunge.) When subjected to drv 
distillation, they gave off a large quantity of carbolic apid undeoompose4? 
(Bunge.) So likewise their aqueous splntion, even when mi^ed ^ith a 
large quantity of potash, gives off, when boiled dowii to a ponsiderable 
degree pf concentin^ion, a large quantity of creosote with the watery 
vapours. (Beichenbach.) The mpre concentrated solution becomes red 
apd f^fterwards brown-yellow by exposure to the air, even in the cold; 
a more dilute ^Iqtiqn, only when hoated« (Beichenbach.) Aolds separate 
the carbolic acid from the salt, this effect being produced even by the 
pl^rhonie acid in the air acting npon the solution. (I^ichenbach.) The 
crystals deliqnesce on exposure to the air (Reichenbiich), and dissolve 
very readilj in water, alcohol, and ether. (Laurent.) 

Dry carbolic acid dissolves dry carbonate of potash, witboat eliminating carbonic 
add, even witU the aia of heat. (Rnnge.) 

Carbolatfi of Soda, — 1. Kr. in contact with sodium evolves hydrpgen, 
fnd forins an oil which does not crystallise by itself, but, if covered with 
a thin liayer of water, forms crystals at the surface of contact. — 2. Kr. 
mixed with a very strong solntiop of soda, hecopies heated &nd forms a 
thip solntion which oi^ pooling solidifies into a soapy mass of indistinct 
crystals. These crystals melt to aq oil when heated. They dissolve very 
readily in water, are insoluble in soda-ley, but dissolve in creosote, 
forcing a thipk mass. (Beichenbach.) 

Carbolate of Baryta, -r-l^ Baryta- water boiled with Ph. till the excess 
of the latter i§ expelled, and then left to evaporate in vacuo at ordinary 
temperatures, yields a crystalline crust, containing 42*48 p. c. baryta, 
and therefore probably consisting of G^'H'^fiaO' + d Aq [2 Aq]. This 
salt yields by dry distillation, first watef, and then a colourless oil which 
has a sweet and 'burning taste and contains carbolic acid. (Laurent.) 

Carbotate of Lime. — Carb. forms with thick milk of lime, a thin 
svrup which dissolves readily in a larser auantit3r of water, fprmina a 
clear thin liquid, just like that which is formed immediateljr with thin 
milk of lime. This liqpid, after being mixed with as much milk of lime 



152 BENZBNE I PRIMARY NUCLEUS CUH«. 

ftB will dissolre iu it^ contains 48*35 pts. [3 At. )] lime to 100 pts. [2 Ai] 
of tbe drj acid. A large quantity of alcohol added to it, throws down 
white crystalline grains solable in water. By continued boiling, it gives 
off carbolic add, and deposits, together witn carbonate of lime, a salt 
containing excess of base, while the liquid, as it cools, deposits a more 
neutral salt in beautiful crystals. Carbonic acid throws down nearly all 
the lime from the milk of lime solution. (Kunge.) 

Cat'holate of Lead, — a. Sesquihasie, Subacetate of lead is ponred 
into aqueous carbolic acid, which must remain in excess, and the preci- 
pitate, which resembles chloride of silver, washed and dried. The white 
powder becomes jellowish at 138% cakes together and melts at 200^ 
into a greyish black mass, which contains 65*08 p. c. lead-oxide (3 At 
oxide to 2 At. acid^; and at a higher temperature, boils up, leaves a 
black residue, and gives off carbolic acid, colourless and neutral at first, 
afterwards yellow and reddening litmua (Ruuge.) — IT. (Volckel, Ann, 
Pharm. SB, 97; and Gorup-Besanez, Ann. Phamt, 96, 54) obtained a 
sinjilar compound by adding a dilute and slightly ammoniacal solution of 
neutral acetate of lead to a solution of creosote in absolute alcohol, 
previously mixed with strong ammonia and diluted with a large quantity 
of water. Yolckers salt contained (mean) 27*34 p. c. C, 2*52 H, and 
63*79 PbO, whence Volckel deduces the formula, PbO,C"H"0* + 2PbO. 
Gorup obtained 64*52 p. c PbO, and gives for his lead-salt the formuht, 
PbO,C**H"0' + 2PbO. Both these formulie are highly improbable, 
Gomp however observes that the first portions of the precipitate obtained 
by fractional precipitation contained less oxide of lead than the latter 
portions; and moreover that such lead-compounds are for the most part 
variable in composition and very apt to decompose. The creosote used 
by Gorup in the preparation of his lead-compound had been boiled for 
7 days, 5 hours each, with strong solution of potash (see p. 145). T 

5. Nevtral /—When subacetate of lead is added to alcoholic carboHo 
acid, only so long as the precipitate redissolves on agitation, the solutioa 
left to evaporate, and the watery liquid, which contains acetate of lead, 
decanted, there remains a transparent colourless oil, consisting of neutral 
carbolate of lead, which dissolves clearly in alcohol, but is resolved by 
water into a precipitate of basic salt, and aqueous carbolic acid con* 
taining a small quantity of lead-oxide. The salt a likewise dissolves in an* 
hydrons carbolic acid, forming a syrup, which dries up to a varnish on 
exposure to the air, dissolves in alcohol, but deposits a basic salt whea 
treated with water. (Runge.) 

Lead-oxide forms with boiling Ph. a very thick liquid, which, on 
addition of a single drop of alcohol, solidifies into a white mass somewhat 
soluble in boiling alcohoL (Laurent.) 

Carb. colours ferri4: itdphate lilac and forms a yellow precipitate, 
(Runge.) Kr. has no visible effect on solution of ferric chloride. 
(Gomp-Besanez.) Kr. imparts a blue colour to very dilute solutions of 
lerric salts, (Deville.) — Cuprio hydrate heated with Kr., first gives off 
its water, and then dissolves forming a brown solution. Cupric acetate 
dissolves sparingly in cold, more readily in hot Kr. forming a brown 
liquid, from which an excess of the copper-salt throws down all the oxide, 
the acetic acid taking up the whole of the creosote. — Corrosive szthlimate 
disolves abundantly and without decomposition iu boiling Kr., separating 
out for the most part on cooling. (Reichenbach.) Nitrate of silver 
dissolves abundantly in cold Kr., bot tue limpid solution assumes a violet 



BOSOUC ACID. 153 

eolonr between 80" and 40^ and at a boiling beat, deposits all tbe silrer 
in the metallic state. (Reichenbachi) Concentrated chloride qf gold 
mixes nndecomposed with cold creosote. (Reichenbach.) 

Carbolic acid mixes in all proportions with dtedhcl and ether. 
(Reichenbach, Rnnffe^ Lanrent.) Similarly with actf^tc efAer. (Reichenbach.) 
A few drops of alconol or ether are sufficient to prevent the crystallisatiou 
at ordinary temperatures. (Laurent.) The solution of 1 vol Kr. in 10 
ToL absolute alcohol is rendered tnrbid at 20^ by the addition of 12 vol. 
but not of 11 vol. water. (Reichenbach.) 

Kr. mixes in all proportions with (leetic acid of sp. gr. 1*070 (also 
Ph. with strong acetic acid: Laurent) j and dissolves in the dilate acid 
much more abundantly than in water. It dissolves in 17 pts. of a cold, 
and in 10 pts. of a warm mixture of equal pts. of glacial acetic acid and 
water. Its solution in 20 pts. of the strong acid is not clouded by water; 
from a solution in very dilute acetic acid, the creosote is separated by 
Glauber's salt. (Reichenbach.) It dissolves a large quantity of aceteUe 
of ammonia; also at a boiling heat, large quantities of the acetates of 
potashy soda and fivtc, which crystallise out on cooling; and acetate of 
lead (which dissolves even in the cold) so abundantly, that the solution 
on cooling, solidifies into a mass composed of needles. (The acetates 
of baryta, strontia, and lime do not dissolve in creosote). (Reichenbach.) 

The solution of crystallised oxaUc, tartaric or racemic acid in boiling 
creosote, solidifies in the crystalline state on cooling. Succinate of 
ammonia dissolves in boiling creosote. Uric acid does not dissolve in it 
(Reichenbach.) 

Creosote dissolves picric, benxoic, citric, oleic, margaric, and stearic 
acids; mixes with volatile oils; dissolves naphthalin, common camphor^ 
stearin, spermaceti, cholesterin, oerin, myricin, and paraffin, many resins, 
indigo and many other colouring matters, and many alkaloids; it coagu- 
lates albumen; precipitates a concentrated solution of gelatin {RungeS\ and 
prevents or retards the putrefaction of animal substances. (Reicheno«ch.) 



Appendix to CarboUe Add*, 

!• Bo8olicAcid» - 

BuKOE. (1834.) Pogg, 81, 70» 

Formed from an unknown substance contained in coal-tar, on heating 
that body with alkalis. When the tar is shaken up with milk of lime, 
and the colourless or yellowish filtrate boiled for some Hours, it assumes 
a dark red colour, and, after a few hours, deposits a dark red powder 
consisting of rosolate of lime. 

Preparation. The brown-black pitch (p. 142) containing rosolic and 
brunolic acid, which remains to the amount of one-third in the distillation 
of impure carbolic acid with water, is boiled with water as long as 
carbolic acid continues to volatilise; then dissolved in a small quantity of 
alcohol; milk of lime added; the rose-coloured solution of rosolate of 



ISi BBNZBMB : PPIMAKT NUCLEUS C»H«. 

Iiiii0 filterpd fnnKk tbe pf0omitei0d bruvoUte of Ume; tho fotoHo »aid, 

$tiU containing branqlio acid, preoipitatef] iherefrpm bj acetic acid; and 
this precipitate tVMted in like mamier with alool|ol, limCi and ^w%io 
acid, as long as the lime produces any precipitate of brunolate of lime. 
The ^sqlic acid precipitated bj the acetic acid is then collected on a 
^Iter, dissolr^ in alcohol after washing aiid drjing^ %od the alcohol left 
\o evaporate. 

Yellow ish-redj pulrerisable resin. 

Hoiolate of lifM separates frqm its aqueons soliition evaporated to i^ 
syrnu, on the addition of ^ pt. ydoobol, in deep red crystals. 

xtosolio acid forms with appropriate mord^i^ts, |ieautiftil red lakes 
and coloured tissues. (Runjg;e.) 

By supersaturating with bydroohlorio acid the precipitate of bmnolata 
of lime obtained in the purification of rosolate of lime, and repeatedly 
treating the brunolio acid which falls down ii^ brown flakes, with lime 
and hydrochloric acid, to remove all the rosolio acid, then dissolving in 
soda, precipitating from the filtrate by hydrochloric acid, and evapo- 
iatinj[ the alcoholic solution, pure Brunolic acid is obtained. (Runge.) 



2. Taurylic Acid, 

Stadblbr. Ann. i^v'oi. 77, 17. 

« 

Tautylie acid. Carbolic acid occurs in the urine of cows, horses, and 
man, together with taurylic acid, which appears to contain 0*H' more, 
and therefore to be 0^'H^O*, but has not yet been completely separated. 
To obtain the mixture of the two acids, cow*s urine is boiled with lime; 
the decanted liquid evaporated to one-third, supersaturated when cold with 
hydrochloric acid, separated after 24 hours from the crystallised hippuric 
acid, and distilled; the distillate, which is clouded with greenish and 
yellowish drops of viscid oil having an offensive odour, distilled with 
excess of potash, (whereupon a neutral azotised oil, heavier than water 
and smelling like rosemaryi, passes over together with a little ammonia); 
the residue mixed with a quantity of sulphuric acid sufficient to neutralise 
only { of the potash (so that no hydroQhlorto or benzoip add may btf 
given o£f); the liquid distilled as long as that which passes over preci- 
pitates b^ic fkcetate of )ea4i thft distillate, which smells exactly like 
carbolic aci49 repefttpdljT rectified over common qaUf till only a small 
quantity of watery liouid is foqnd mixe4 with the oily distillate; these 
two liquids repeatedly shaken up together ^r twelve hours with 
carbonate of soda (to remove damaluric and damolic acid, which impart 
a strong acid reaction); the oil, which remains in diminished quantity, 
extracted from the mixture by ether; the ether distilled off; the oily 
residue distilled with strong potash-ley (whereupon a small additional 
quantity of neutral oil passes over); the residue distilled with bichromate 
of potasli;and th^ oil which distils over, set aside for some time in contact 
^iu^ chloride of calcium^ find di^till64 tfiexefrom^ iirith freauent change 



^ 



9U|iPH6BBKZOLIG AOIQf lfi(t 

of receiFer. It then begina to distil ^t 170°, at which tampemtiiM ufater 
still paeseff oves together with the oil; at )8Q^ oil ia obtained still 
retaiuiog wf^^' in solutiqiij from that jpoint to 195° the largest and 
purest port|oii of oil] and at 200°^ brownish oil. (Stadeler.) 

The mixtore of carbolie apd ^ofjljo acid obtained bet^eeii 180° and 
195° is a coloarless oil which does not solidify at — 18°; boils at a some- 
what higher temperature than carbolic acid; smells exactly like casto* 
reuiui makes a white spot pn the skin and then caoses desquamation; ^nms 
firwood blu^ on addition of hy4]*ochlorio acid; and when adfied to soli;tio9 
of ferric chloride, first turns it blue and then produces a light-coloured 
precipitate. Its mixture with an equal volume of oil of yitnol solidifies 
into an arborescent fnaQ0> the mother-liquor of which contains carbolic 
acid. When boiled with nitric acid^ it yields a large quantity of picric 
acid. (Stadeler.) 

Staddety 
Taurylic acid, 
atlSO*. 180**— 195". at 195**. 
14 C 84 .... 77-78 74-90 .... 771 .... 77-14 



8H 8 .... 7-41 7-61 .... 7-4 .... 7-56 

16 .... 14-811 ,..,o 15.6 14-67 



C»*H«0« 108 .... 100-00 10000 .... 100-0 ,.., 100-00 

Hie nitrogea in St&deler's analysu ariaes from admixture of the nentnd oil abovt- 
meDtioned. 

This compound Is isomeric with hydrate of cresyl (p. 146). 



Cot^ugaUd Compoundi of the Primarjf NwiUm Q^W-, 

SulpbobfiPfoUc Acid, 

MlfMHEBLIOH. (1834.) Pcg^- V^i ^^^ ^^ ^^^^ 

satire, BensBidunterfchwrfeU'dure, Funetejiwefelf^if Acid$ ben909uffttriliue. 

Formatum. From benzene and anhydrous sulphuric acid or fuming 
oil of vitriol, (p. 138). 

Preparation. Benzene is added, with agitation and frequent cooling, 
to fuming oil of vitriol contained in a bottle, as long as it dissolves; the 
solution diluted with water, filtered from the sulphobenzene, and satu- 
rated with carbonate of baryta; the filtrate precipitated by the exact 
amount of cupric sulphate required (because the copper-salt crystallises 
better than the barium-salt); the filtrate evaporated till it begins to crys- 
tallise; the cfTstals collected after coolings decomposed by sulphuretted 
hydrogen; and the filtrate evaporated to a syrup, and cooled. 

Properties, CryBtftUine inasf . 



156 DBNZBNB : PRIMARY NUCLEUS C»U«. 

CambinaUoni. The acid disBolves in wUer. 

The SulphohemclateB require a etrong heat to deoompoae them. When 
boiled with excess of a fixed alkali, thej are not merely reoolred into 
benzene and a sulphate of the alkali, hot likewise jrield other products. 

The sulphobenzolates of ammonia^ paUuh, 8oda, ferr<nu tmcUg ginC" 
cxide and sUvtr-oxide crystallise rery welL 

BaryfO'iaU. -— Crystalline crusts ; (Mitscherlich); white crystalline 
powder, appearing under the microscope to consist of four-sided ihombic 
tables. (Gericke, Ann. Pharm. e, 208.) 





... 720 
5*0 
... 68*6 
... 32*0 
... 48*0 


.... 31*92 
.... 2-21 
.... 30-41 . 
.... 14-18 . 
.... 21-28 


Bndcton 
& UoAnuuu 

*..•••. uU-38 «••• 

....... Av X«r 


Gericke. 


• B». 


30*36 


2 S 




6 O 









C»H*Ba,2S0* 225*6 .... 10000 



The copper-tall forms laige crystals, which giye off all their water at 
170^ and do not suffer any further decomposition even at 220"*. 
(Mitscherlich.) 



12 C 

5 H 


DrM at 180*. 

72 .... 38-10 . 

5 .... 2*64 . 


HitacherUch. 

38*28 

2-64 


Cn 

2 S 

6 


32 .... 16-93 . 

32 .... 16-93 . 

48 .... 25*40 


16-44 

16-83 









C>»H«Cn,280» 189 .... 10000 

Sulphobemolate of EtJiyl C»H»(OH»),S*0».~ Formed by heating the 
lead-salt with iodide of ethyl to 100° in a sealed tube. From an alcoholic 
solution evaporated over oil of vitriol, it crystallises in slender needles 
which are not volatile. Heated with potash, it is resolved into alcohol 
and sulphobenzolic acid; also when the aqueous solution is rapidly con- 
centrated by evaporation. Dissolves readily in water, less readily in 
akohoL (Gericke, Ann. Fharm. G, 216.) 



%• Bisulphobenzolic Acid. 

C»H«S*0» = C»H«,4S0*. 

BucKTON & HoFMANif. FhiL Tram. 1856; abstr. Chtm. Soe, Qu. J. 9; 
Froc. Boy, Soc, 8, 158. 

Formation and Freparation. 1. By the action of sulphuric acid upon 
henzonitrile, sulphobenzoic acid being produced at the same time : 

C"H»N + 6HS0< - C"H«S<0» + H(NH<),2S0* + 2C0« ; 
and: 

C"H*N + 4HS0< + 2BO - C"H«S«Oi« + H(NH<),2S0«. 



SULPIIOPHBNIC ACID. 157 

Tbe action is not attended with great evolution of heat; and no gas is 
eyolTed till tbe temperature is yerj considerably raised, wbereupon 
benzoic acid sublimes in tbe neck of tbe retort, carbon is deposited, and 
sulpburons acid evolved. Tbe action was continued for some time after 
the appearance of the sulphurous acid, in order to decompose the sulpho* 
benzoic acid as much as possible; on cooling, a semi-transparent, bard 
mass having a glassy fracture remained in the retort This mass boiled 
with water and carbonate of baryta, evolved ammonia and yielded a 
mixture of sulphobenzoate and bisulphobenzolate of baryta. The dark* 
coloured filtrate was then again decomposed by sulphuric acid, boiled 
with excess of oxide of lead, filtered, and the filtered liquid treated with 
snlphuretted hydrogen. The greater portion of tbe colouring matter was 
carried down with the sulphide of lead; and on saturating the acid liquor 
with carbonate of baryta, evaporating nearly to dryness, redissolving in 
water, and adding alcohol, a precipitate was obtained consisting of 
disulphobenzolate of baryta^ mixed however with sulphobenzoate, the 
greater portion of the latter salt remaining in solution. — 2. By the action 
of fuming sulphuric acid upon snlphobenzolic acid. The latter acid 
(obtained from the lead or copper-salt^ is dried on the sand-bath till it 
emits white fumes, and exhibits a slight brown colonr, indicating inci- 
pient decomposition. It is then introduced into a dry retort together 
with an equal volume of strong Nordhausen sulphuric acid, and the 
mixture heated to the boiling point for two hours. The liquid is then 
evaporated to nearly the original bulk of the snlphobenzolic acid used, 
and the resulting bisulphobenzolic acid decolorised by treating it with 
oxide of lead, and decomposing the filtrate with sulphuretted hydrogen* 
On saturating the colourless acid thus obtained with carbonate of baryta, 
and evaporating, an apparently amorphous baryta-salt is obtained, which 
however under the microscope, appears distinctly crystalline, exhibiting 
minute shuttle-shaped forms, which are generally densely grouped toge- 
ther. This salt is very stable, but when strongly heated on platinum 
foil, it burns and gives off sulphurous acid* 

Backton & Hofinann, 
(1) at 170*. (2)atl95^ 

12 C 72 .... 13-30 

4 H 4 .... 1-07 

2 Ba 137 .... 36-72 3770 .... 36-43 

4 S 64 .... 17-16 .... 17-35 

12 96 .... 25-75 

C»H*Ba»S<0» 373 .... 100-00 

Tlie salt (1) still coatained sulphobenzoate of baryta, although it had been partiallf 
purified by repredpitation with aloohoU (Backton i Hofinami.) % 



Sulphophenic Acid. 

C"H*S»0* =5 C»H«0»,2S0\ 

Laurbnt. (1841.) ilT. Ann, Chim, Phys. S, 209; also J. pr. Ghent. 
25f, 408. 

CMiohckiatfeMvre, Suijbphanistdure, AM9 tulfophtmique. 



1 58 BENZENE t 0XT6BN NUCLEUS C^H^O*. 

Formatwn and PreparaHoH. The mi^are of earbolie field with 
ezeesfi of oil of Titriol (p. 147), is mixed with water after standing for 
24 hours, and satnrated at the boiling heat with carbonate of barrta; 
the filtrate evaporated to the erjstallising point, the orjstals purified by 
recrjBtallisation from boiling aleohol; the needles of salphophenate of 
barjta eoUeoted on a filter, washed with a small quantity of aloohol^ and 
decomposed by an equivaletat quantity of dilate snlphuric addj and thd 
filtrate evaporated in vacuo. 

By saturating the acid with ammonia, the ainmonia-^U is obtained 
in small scales which contain 89*74 p. c. sulphuric acid^ and are there- 
fore C»H«(NH')0',2S0* 4- Aq. When boiled with nitric aoid, they yield 
picric acid in large quantity. 

The needles of the batyta-eaU lose 9*1 p. e. ^8 At) Water at 200'' id 
vtotto; give off carbolic acid by drr distillation; and at A red 
heat leave 42*48 p. c. sulphate of baryta; whenee they are &= 
C"H»BaO*,2SO* + 8 Aq. [dr 4 Aq. ?] (Laurent.) 



Oi^ffhi-nudenk 0"H*0*. 

Kinone. c"H*o* a c»H*o^o^ 

WoSKRESSENSKt. (1888.) AfitL Pharfnt. 27, 2^8; /. pr. Chm, l8^ 

419; 34, 251. 
WbHLBB. Ann. Pharm. 5l, 148. 

Chirum, Chinoyl, Quinonef QuinoUe, 

Formation. 1 . Sublimes when the sails of kinic acid are bnmt at a 
gentle heat-^ 2. More Abundantly when kinic acid is heated with man- 
ganese &tid sulphuric acid. ( Woskressenaky) — ^. In a similar manner also 
from caffeio acid, and therefore froiii the leaves and beans of the coffee 
plant, the leaves yielding the greater product; also under similal* circum- 
stances front the peculiar acid of Paraguay tea; from the leaves of the 
common holly (Ilex aquifoKum); the leaves and branches of privet 
(Lt^uOrum mtlgare); from ivy; from the evergreen oak (Quereus ilex), 
the common oak (Querctu roSur); the common small-leavea elm (Ulmut 
campegtris), the ash (Fraxinm excelsior), and the Cpd&pia latifolia, a 
leguminous plant from the Cape of Good Hope. It was only however 
from the leaves ^nd berries of the coffee^planl and from the holly that 
the kinone was obtained in crystals; in the other cases, its formation 
was concluded from the deep yellow colour of the distillate which passed 
over at a comparatively low temperature, and from the dark humus-like 
colouring produced in that distillate by aihmonia. No kinone was 
obtained from the laburnnm) from tobacco> from the sloe (Prunus apinosa), 
and from many other plants not specified. (Stenhouse, Phil. Mag. J. 
[4] 7, 21; Ann. Pharm. 89j 244:) % 

Preparation. 1 pi of kinic acid [or coffee: Stenhou»e\ is distilled 
with 4 pts. peroxide of manganesOi 1 pU oil of vitriol and ^ pt» water, 



KINO!ie» 150 

_»oii tlift inixinre froths ap and gites off defase impoofB which 
condense in the cooled receiver in golden yellow neediest and these 
^Btalfl are purified h^ pressore between paper and. repeated sublimation. 
(W oskieflsensky.) l*he proportions just given mast be strictlj observed; 
if the mixture is too thin^ it froths over. Instead of kinie aoid> kittatd 
of lime maj bo usod, even the sjrupj salt obtained from quiniiie manu- 
&etories. If more than 100 grammes of kinio acid are operated upon 
at once> the mixture beoomes tod hotj so that, in spite of the best con- 
densation, a large portion of the kindne is carried a^aj by the hot 
carbonic acid. x£ a rerf capacious flaisk is used^ fitted trith a tube 8 ft; 
long which leads into a well-cooled receiver^ and the fire removed as 
soon as the action begins, the mass becomes sufficiently heated to ensure 
the continuance of the action, and the greater part of the kihone is 
deposited in needles in the tube. These needles are rinsed out of the 
tube with the watery distillate in the receiver, which contains kinone and 
formic acid I Washed several times on the filter with cold water; then 
pressed; and dried over chlorldo of calcium within a bell-jar. (The dis- 
tillate is well adapted for the preparation of green hydrokinone, which 
may be obtained by mixing it with a quantity of sulphurous acid not 
sufficient to decompose it completely.) (Wohler.) 

. Properties, 'Wheii sublimed, it fpmis transparent, gold-yellow, long, 
shining needles (Woskressensky); after crystallisation from hot water, 
it is darker, of a dingier yellow colour, and less transnarent. (Wohler.) 
Heavier than water; melts at 100^ to a yellow liquid (Woskressensky), 
which crystallises on cooling. (Wohler.) Volatilises without alteration 
(Woskressensky)^ and sublimes, even at ordinary temperatures, from one 
part of the containing vessel to JGinother. (Wohler.) Has a pungent and 
persistently irritating, tear-exciting odour. (Woskressensky, Wohler.) 
A gramme of it taken internally has no effect upon dogs. (Wohler & 
Ferricki^ Ann. Pkarm, 65, 843.) The aqueous solution imparts to the 
skin (by decomposition) a brown colour which cannot be removed by 
washing. (W5hler.) Neutral to vegetable colours. 

Woskresaenskyi Wlttiler. Laorenti 

18 d .:;;....;i;i..l. It i:.: 6B'67 .;;..;.. 67*31 :....;.4 67-0f :*. i 66-4 

4H : .4 ;... ^-70 .». 37S 3-7Q u Z'1 

A 6 ;.... si .... 29-y 28-90 2d-93 299 

C»H*0«,0* .... 108 .... 100-00 100-00 w.imi lOO'OO :....u iOO-O 

• GSm^re UttMi {VoM^ rM. tlMh ^i tMi^ (Aim. 1B49) 190) \ Wittiler 
(Ann. Phtarm. 65> 349). 

Decompositions. 1. The aaueous solution of kinono acquire by 
ciposard to tiie air^ fk opntinuauy deeper yelloWbh red colour, and \ilti- 
i^iately dbpofeiU a black-brown mouldy substance.. (Wbhleh) The 
aqueous solution mixed with ammonia or potl^sh absorbs Oxygen ana 
assumes s^ black bfpwn colour on exposare to the air^ and then forms 
with acids a black mouldy precipitate, very sparingly soluble in Wat&lr 
and alcohol (Woskressensky); doubtless consisting of melanic acid : 
C»H*0* + 20 = C"H^O». (Laurent, Compt. rend. 26, 35.) — 2. With 
dry chlorine gas, kinone forms terchlorokinone, the action being attended 



,' 



160 BENZENE: OXYGEN-NUCLEUS C^'H^O^. 

with great rise of temperatare and evolution of hydrochloric acid. 

(Woskressenskj): 

c»H<o« + ea - c»c»*Ho« + 3Hcl 

d. Heated with hydrochloric acid and chlorate of potash, it is quickly 
conrerted into chloraniL (Hofmann, Ann. Pharm, 62^ 65.) — 4. Oil of 
vitriol carbonises kinone. nVoskressenskj.)— 5. Strong hydrochloric acid 
colours kinone brownish olack, and then dissolves it, forming a red- 
brown, afterwards colourless liquid, which no longer smells of kinone, 

but contains chlorhydrokinone CCIH'O^ (W&hler.) [The first prodacts 
are probably kinhydrone and chlorkinhydrone, the presence of both of whidi in the 
black ma^a formed at the begioniog of the action, was pointed out by Stftdeler. 
{Ann. Pharm. 69, 308): 

4C»H«0* + 2HC1 - C»<H»08 + C?*CPH«€)»j 

and these compounds, by the forther action of the hydrochloric add, are converted 
into chlorhydrokinone, being at the same time dissolTcd and decolorised : 

C"HWO» + CWCPHH)8 + 2HC1 - AOHABH}*}. 

St&deler gives a different explanation of the process. — Chlorhydrokinone is like- 
wise formed by the action of hydrochloric acid gas upon dry kinone. 
(Wohler.) — 6. Ammoniacal gas passed over kinone, quickly converts it, 
with separation of water, into emerald-green crystalline hinonamide, 
which forms with water a nearly black, quickly decomposing solution, 
and contains 63 '06 p. c C and 4*96 H, and is therefore perhaps 
C"NH«0» [or C"NHK)«1 (Woskressensky : comp. Gerhardt, Compt. 
Chim. 1845, 191.) — 7. Sulphuretted hydrogen gas has no action upon 
dry kinone, but when passed through the cold aqueous solution, first 
reddens it, and then throws down brown fiakes of orown sulphohydro- 
kinone, which, if the passage of the gas be still continued, and especially 
if the action be aided by heat, is converted into yellow sulphohydro- 
kinone. The same compound is formed when bihydrosnlphate of 
ammonia is poured upon kinone. (W&hler.) — 8. Kinone dissolved in 
water is converted into hydrokinone by excess of hydriodic or hydro- 
telluric acid, with precipitation of iodine or tellurium, and by sulphurous 
acid, with formation of sulphuric acid. (Wohler.) —- Dry eulphurous 
acid gas has no action upon dry kinone; and even phosphuretted 
hydrogen, arseniuretted hydrogen, and hydrocyanic acid are without 
action upon it. (Wohler.) 

Comhinations, Kinone dissolves with some difficulty in tpoter. 
(Woskressensky.) 

It dissolves with yellow colour in dilute hydrochloric or nt^rtc acid* 
(Woskressensky.) 

Its aqueous solution throws down from basic acetate of lead a pal0 
yellow jelly, but does not precipitate the neutral salts of lead, oopper, 
or silver. (Woskressensky.) 

Kinone dissolves with tolerable facility in alc(Aol and eAff\ 
(Woskressensky.) 



HTDROKINONB« 161 



Hydrokinone. 

WOfluia* dnn4 Pharm. 46, 854; 61, 150. 

CoUmrlm fffdroHnoiu,farblo9e$ HydroeMn^n, ffydr^quimHt (ne^ioMi 

FormaiioH. 1. Thtt obief prodnot of tbe dry disiilUiioti of kiiild 
aoid. -^ S. Fortood &l«o by treating kioooo witb hydriodio Mtd, bydr<V> 
tellorio acid, or largo qaantitios of aqueoiii ftttlpburotMi aoid^ ^t protd^ 
oblorid« of tin. 

Preparation, 1 . Tbe distillate mixed witb solid particles, wbiob ii 
obtained by tbe dry distillatioD of kinic acid, is filtered from tbe tar^ and 
again, after cooling, to separate bensoio acid; tbe yellow, beavy, oily 
mixture of benzene, oarbolid acid and salicyloos acid, distilled from tbe 
filtrate; tbe brown residue in tbe retort evaporated and left to cool till 
benzoic acid crystallises oat; tbe motber-liqnor dilated witb water, wbich 
makes tbe liquid milky and separates iar; and tbe resttlting filtrate 
evaporated till tbe bydrokinone crystallises out. «^ t. Sulpburous acid gas 
is passed tbrouffb warm water saturated witb kinone, and baving kinone 
also suspended in it, till all the kinone is dissolved, and tbe liquid appears 
colourless; tbe solution tben gently evaporated to tbe crystallising point; 
and tbe crystals purified by preasuro and recrystallisation. — It is not 
necessary previoosly to remove tbe sulpburio acid by carbonate of baryta. 
— A saturated aqueous solution of kinone may also be mixed with 
aqueous bydriodio acid, and tbe watery liquid, after filtration from tbe 
iodine, evaporated to tbe crystallising point 

Properties. Transparent, colourless, stx-slded pfistnsi trith oblique 
terminal faces. Easily fusible, orystallisfng on cooling. Sublimed wben 
heated, in shining laminsa like benzoic acid. InodoroQs j hAd a swedlish 
taste ; neutral to vegetable colours. 

Schnadermaiui. 

12 C 7a „.. 65-45 65-91 

6 H 6 .... 5-46 5-53 

4 O 32 .... 29-09 28-56 

C"H«0>,HK)« no .... 100-00 ...*.... 100-00 " 

Hay be itgftrded at an tloohol. 

Deeompoiitions. 1. HydrokinoiiO enddeolv beated above tbe boiling 
point, is p^utially decomposed into kinone and green kinbvdrone. [What 
becomes of the excese of hydrogen ?] — 2. Chlorine, chromate of potash, sesqui- 
chloride of iron, or nitrate of silver, converts bydrokinone dissolved in 
Water into green needles of kinbydroue, with formation of bydroohlorio 
acid, chromic oxide, or protochluride of iron and bydroohlorio acid, or 
with precipitation of silver. — 8. Tbe aqueous solntiou of bydrokinone 
imparts a saffron-yellow colour to cupric acetate, and when heated throws 
down*ouprous oxide, kinone^ volatilising at tbe same time. «— 4. With 
VOL. xi. * _ M 



162 



BENZENE: OXYGEN NUCLEUS C^^H^O^. 



ammoQja It immediately assumes a browu-red colour, and on subsequent 
evaporation leaves a brown mouldy mass. 

Combinations, Hydrokinono dissolves easily in water, especially 
when hot. 

HydroiidphaUof Hydrohinone, —a. ^»6anc.— Sulphuretted hydrogen 
gas passed through a saturated aqueous solution of hydrokinone at iff, 
produces very long colourless prisms* 

6. Sesqmbasic, — When a solution of kinone is saturated in the oold 
with sulphuretted hydrogen, small shining crystals immediately separate 
from it, which dissolve when heated (supposing the stream of sulphuretted 
hydrogen to be kept up), and on cooling separate in transparent colourless 
rhombohedrons, which resemble those of calcspar, and after pressing 
between paper, and drying in vacuo, are inodorous and permanent in 
the air. 



24 C 

13 H 


Cryttala a. 

144 

13 


.... 60*76 
.... 5*48 

6*75 .. 
.... 27-01 


Wohler. 


S 


^ 16 


6-78 


8 O 


64 




2C»H«0*,HS. 


*i%f 


.... 100*00 

.••. 59*04 t. 
.... .5-50 .. 
»•• «J*79 .. 
.... 26-37 .. 




36 C 


216 


WtfUer. 
58-70 


20 H 


20 


5-51 


2 S 


32 


8*86 


12 




26-93 









3C»H«0<,2HS 364 .... 10000 10000 

Both kinds of crystals, when melted per »e, or moistened in contact 
with the air, or when their aqueous or alcoholic solution is boiled, give off 
sulphuretted hydrogen and leave hydrokinone. 

Hydrohinone wUh Acetate of Lead. — * A solution of hvdrokinone in 
warm, moderately concentrated aqueous acetate of lead, deposits, on 
cooling, oblique rhombic prisms, which give off 5*23 p. c. (nearly 3 At) 
water over oil of vitriol. (Wohler, Ann. Fharm. 69, 299.) 



AfT'dried cryttaU* 

20 C 120 

15 H 15 

2 PbO 224 

13 O 104 



Wohler. 

25*92 26*34 

3*24 3*10 

48*38 47-33 

22*46 23*23 



C"H«0<,2C<H»PbCM + 3Aq.... 463 ..,. 100-00 



100*00 



The aqueooB mixture of kinone and nentral acetate of lead, yields, on gradoal 
addition of ammonia, a pale yellow precipitate, which soon rinks together in the form of 
a grass'green powder, appearing under the microscope to be composed of tranrittoent 
spherules* In drying, it turns brown and gives off an odour of kinone. 

Hydrokinone dissolves readily in alcohol and in ether. (Wohler.) 



r 



MELANIC ACID. 163 

Melanic Acid. 

C»HW = C»H*0«,0*. 

PiRiA. (1839.) Ann, CMm, Phy$. 69, 281; also Ann. PJiarnu 

30, 167. 
WosKRESSENSKY. J, pr. Chem, 34, 251. 
Laubent. Compt. rend. 26, 35. 

Melaiudure, Chinons&ure, Adde melanique. 

I'ormatioti. By the action of the air on kinone, or hydrokinone 
dissolved in aqueous potash or ammonia (p. 159), or on an aqueous solu- 
tion of salicylite of potash. 

Freparation. 1. An aaueous solution of kinone mixed with potash 
and exposed to the air till it turns black, yields with hydrochloric acid 
a black mouldy precipitate, which is to be washed and dried. (Woskres- 
sensky.) — 2. Moistened salicylite of potash is exposed to the air till it 
IS blackened through and through, and the acetate of potash formed at 
the same time is dissolved out by water. (Piria.) 

Properties. Black tasteless powder, resembling lamp-black. (Piria.) 

Piria. Woskressensky. 



12 C 

4 H 


72 

4 


.... 5806 ... 
.... 38-71 ... 


..i.. 0/ *4 ... 

4-01 ... 

38-75 ... 


56-65 

3-30 


6 O 


48 


40-05 








C«H<0« 


124 


.... 100-00 .... 


10000 ... 


100-00 



So according to Laurent's view (Compt. rmd. 26, 35) ; according to Piria, it it 
C»HH)*; according to Woskressensky, C»H«0». 

Decomposition. The acid bums without flame and without residue. 
(Piria.) 

ComMnatxons. Insoluble in water. (Piria) 

The acid dissolves with effervescence in alkaline carbonates, and is 
precipitated therefrom in its original state h^ stronger acids. (Piria.) 

Silver-salt, By digesting ammonia with excess of the acid and * 
mixing the filtrate with silver-solution, a heavy black precipitate is 
obtained. (Piria.) 

Piria. 

12 C 72 .... 31-17 27-67 

3 H 3 .... 1-30 1-95 

Ag 108 .... 46-75 48-00 

6 O 48 .... 20-78 22-38 

C»H»AgO» 231 .... 10000 10000 

The formala assumed by Laurent does not agree very veil with Firia's analysis. 

The acid dissolves readily in alcohol and in ether. (Piria.) 

M 2 



164 BENZENE: OXYGEN-NUCLEUS C»H*0«. 



Ccnjuffokd Compound. 

Einhydrone. 
C*H»0« = C»H*0*,C«HK)*. 

WoHLBBy Ann, Pharm, 45^ 354; 51^ 152. 

Green Hydrokinone, Chinhydron, grilnee Bydroekhum, Sydro^hume tcr/e, 
QiUnhydrime, 

Formation and Preparaiion. 1. Immediately precipitated in the 
crjBtalline form, on mixing the aqueous solutions of kin one and hydro- 
kinone. — 2. By combining aqueous kinone witli a quantity of hydrogen 
not sufficient n>r the formation of hydrokinone; «.^. aqueous kinone 
mixed with sulphuric acid at the negative pole of the gafyanio circuit; 
kinone mixed with sulphuric acid in contact with sine; aqueous solution 
of kinone with gradual addition of protochloride of tin or protosulphate 
of iron, or sulphurous acid, or alloxantin, the latter being converted into 
alloxan. — 3. By the partial dehydrogenation of aqueous hydrokiuone; 
e. g. when spongy platinum or animal charcoal moistened with the solu- 
tion is exposed to the air; when chlorine gas is passed through aqueous 
hydrokinone, or that liquid is mixed with nitric acid, chromate of potash, 
sesquichloride of iron, or nitrate of silver. — The mixtures prepared 
according to (2) or (3) with concentrated solutions, assume for a while a 
black-red colour and then become filled with long, green, metallic-looking 
prisms of kinhydrone; but if the solutions are too dilute, the kinhydrone 
remains dissolved and is decomposed, emitting the odour of kinone. — 
The largest crystals are obtained by at once adding to a saturated 
aqueous solution of kinone (or even to its mother-liquor), a quavtity of 
aqueous sulphurous acid Just half sufficient for the lormation of hydro- 
kinone. 

Properties. Very long and thin green prisms, having a metalUo 
lustre (like the wings of gold-beetles or colibri, and brighter even than 
purpurate of ammonia), and appearing red-brown by transmitted light 
when strongly magnified. Melts easily to a brown liqnidi and sublimes 

artly nndecompoeed in green laminss. Smells slightly like kinone^ and 

as a pungent taste. 



E 



24 C 

10 H 


144 

10 


8 


64 



Wdhler. Sehii6(il«rmahtti 

66-05 66-32 66-20 

4-59 4-64 4-62 

29-36 2904 29*18 



C»*H*»d* 218 .... 100-00 10000 100*00 

Decomposiiions. 1. When kinhydrone is heated, it sublimes partly 
undecomposed, partly converted into yellow kinone. — 2. When it is 
boiled with water, kinone distils over, and the remaining dark red-brown 
liquid contains, together with a large quantity of hydrokint>ne, a brown 
tar, which separates, partly on cooling, partly on subsequent addition of 



8ULPH0BENZBNB. 165 

water. — 9. Tbe green solution of kinhydrone in ammonia qnickly 
assumes a dark red-brown colour on exposure to the air, and leaves a 
brown amorphous mass when evaporated. — 4. Kinhydrone is converted 
into hydrokinone by aqueous sulphurous acid, protochloride of tin, or 
sine and sulphuric acid, but not by hydriodio acid or telluretted 
hydrogen. — 5. From a solution of nitrate of silver, on addition of 
ammonia, the aqueous solution of kinhydrone quickly reduces the 
silver. 

dmbinatiom. Kinhydrone dissolves sparingly in cold water, but abun- 
dantly and with brown-red colour in hot water, separating again as the 
liquid cools. 

It dissolves, with green colour, in aqueous atnmoma. 
Its aqueous solution forms with acetate of lead, on addition of 
ammoni%, a bright greenish yellow precipitate, quickly changing to dirty 

It dissolves easily, with yellow or red colour, in alcohol or ether, 
crystallising again in green needles as the liquid evapoiates, (Wbhler.) 



Sulpho^udeui C»H»(SO»). 

Sulphobenzene. 

C»*H»SO* = C»H»(SO»). 

MiTSCHERLICH. (1834.) Poffff. 31, G28. 
H. Gbrickb. Ann. Fhaitn. 98, 389. 

Sulfobenzid, Sulfifune, 

Formation and Preparation. Produced by treating benzene with 
anhydrous sulphuric acid or fuming oil of vitriol {v- 183), and separates 
in the ciystalfine form when the mixture is diluted with a large quantity 
of water ; it is then to be washed on the filter with water, dissolved in 
ether, left to crystallise from the filtrate, and the crystals purified by 
distillation. (Mitscherlich.) 

PropeHies. Crystalline; melts at lOO"* to a transparent, colouriesi 
liquid. Boils between 360'' and 440°. Inodorous. (Mitscherlich.) 

Mitscherlich. 

12 C 72 .... 66-55 6642 

5 H 5 .... 4-59 4*55 

8 16 .... 14-68 14-57 

2 O 16 .... 1418 14-46 



C"H»SO* 109 .... 100-00 10000 

Gericlce doublet the formula of this compound, writing it in the form of an organic 
radical, c»H»sS } °^ •ccount of iU hchavionr with fuming nitric acid 
(p. 166). Gcrhardt writes the formula ; ^"^q^hI}. W this were the true formula, 



166 UENZK2i£: SULPHO-NUCLEUS C»m*(SO»). 

the body should be resolved by potash into benzene and salphopheoate of potaabi 
according to the equation : 

but no such reaction takes place, eyen when the compound is heated to 180° in a sealed 
tube with alcoholic potash for scTeral hours. (Gericke.) 

Decompositiotis. 1. Chlorine and bromine decompose snlpfaobenzene 
when heated with it, the former producing hjdrochl orate of terchloro- 
benzene. — 2. Sulphobenzene detonates when thrown npon nitre or 
chlorate of potash heated considerably above the melting point, but may 
be distilled from these salts without decomposition. — 3. When heated 
with oil of vitriol, it forms a peculiar acid, whose baryta-salt is soluble 
in water. (Mitscherlich.) — IT. 4. Heated with fuming nitric acid, it 
forms a solution from which water throws down a yellow product, sepa- 

rable by hot alcohol into nUrosulpkol&nzene, q^, H'SO' i ^^^^^ dissolves, 

snd binitrimilphobenzetie, Qii-yrrriOQz > the greater part of which remains 

undissolved. The latter compound is produced in much greater quantity 
by acting upon sulphobenzene with a mixture of sulphuric and nitric 
acids. (Qericke.) [Gericke's binitrosulphobenzene might, however, be regarded as 
nitrosulphobenzene, C^^XH^SO^^ and his nitrosulphobenzene as a compound of 
C^XH^SO* with sulphobenzene C»H«SO»]. % 

Combinations* Sulphobenzene dissolves but very sparingly in toaier. 

It dissolves in somewhat concentrated acids, and is precipitated there- 
from by water. — It is insoluble in aqueous alkalis. 

It dissolves in alcohol and ether and crystallises from the solutions. 
(Mitscherlich.) 



Yellow Sulpho-hydrokinone. 

C»H^SO* = C»H*(S0»),H20'1 
WoHLEB. (1845.) Ann. Fhamu 51, 158; 69, 295. 

An alcoholic solution of kinone is saturated with sulphuretted 
hydrogen, which first colours it dark brown and afterwards light yellow; 
and the liquid, after filtration from the slender sulphur-crystals, is eva- 
porated in vacuo : 

[Perhaps thus : C"H^O< + 3HS = C«H'S20< + 2S]. 

If a nearly boiling aqueous solution of kinone is used, the precipitated 
sulphur remains mixed with the product, and appears on the filter, after 
washing and drying, as a pale yellow powder, which turns green on expo- 
sure to the air, and solidifies after fusion into a brown amorphous mass. — 
2. Suluhuretted hydrogen is passed into brown sulpho-hydrokinone sus- 
pended in water at 60** or ditsolved in alcohol, till the substance is entirely 
converted, with precipitation of sulphur, into a pale yellow powder; 

[Perhaps thus ; C^'S^O* + HS = C»-H'SO« + 2S.] 



BKOWN SULPUO-UYDKOivINONi!;. 167 

In this case, sulphur remains mixed with the product. — 3. Kinone, 
immersed in bihydrosulphate of ammonia, forms, with evolution of 
heat, a yellow mass, from whose reddish-yellow solution in wate^ 
previously freed from air b;^ boiling, hydrochloric acid precipitates the 
compound in yellowish white flakes. — 4. Sulphuretted hydrogen is 
passed through water in which kinhydrone is suspended : 

[Perhaps thus: C«H«>08 + 4HS - 2C"H'S0< + 2S]. 

Prepared by (2) : Yellowish crystalline mass, which melts with par- 
tial decomposition at 100°. In the fucoholio solution it has a disagreeably 
harsh and hepatic taste. 



24 C 

14 H 

2S 

80 



C?<HWS*0» 254 







WtfUer (2). 


144 


.... 56*69 . 


., 56-53 


14 


5-52 .. 


4-95 


32 


.... 12-59 .. 


12-54 


64 


.... 25-20 .. 


25-98 


254 


.... 10000 .. 


100-00 



According to Wohler, it is C^^H'S^OS which certainly agrees better with the 
hydrogeni-detOTmination. 

Deoampositions. 1. Yellow sulfhydrokinone bums with the odour of 
sulphurous acid. —-2. Its aqueous solution deposits on evaporation, a 
green sulphuretted compound, and retains hydrokinone in solution. -— 
d. Its aqueous solution forms, with a comparatively small quantity of 
chlorine or sesquichloride of iron, a light brown precipitate, to which a 
larger quantity of chlorine imparts a yellowish red colour. Probably a 
mixture of sulphur- and chlorine-compounds. — 4. When immersed in an 
aqueous solution of kinune, it is resolved into brown sulpho-hydroki«> 
none, hydrokinone and kinhydrone. [Perhaps in this way : 

Combinations, Dissolves spanngly in cold, more abundantly in hot 
tffatei'y which then becomes milky on cooling. 

It forms a white precipitate with neutral acetate of lead. 

Dissolves readily in acetic acid, alcohol, and etker formiuff reddish 
yellow solntions^ and remains in the form of an amorphous residue when 
the solvents evaporate. (Wohler.) 



Brown Sidpho-hydrokinone. 

C»H*S«0* = C"H*(SO*)»,H*, ? 

WShlbb. (1845.) Ann. Pharm. 51, 157; 69, 295. 

Formation and Prepaintion. Sulphuretted hydrogen gas is passed 
into an excess of cold aqueous solution of kinone, aod the precipitated 
red-brown or black-brown mixture of kinhydrone and brown sulfhy- 
drokinone treated with a small quantity of alcohol to extract the latter, 
the former remaining for the most part undissolved; tC"H^O* + 2HS» 



168 BBNZBNB: BROMmS-NUCLBUS C»Bi<H«. 

By eTEporation of the alcobolie aolation: Shinfiig^ tnadaeeni, Mnor- 
photts maos; by precipitation t Dark brown amorphooB powder, inodoroaa 
and tastelesB, bat eaaily fa«ible. 

WtfUer. 

12 , 92 .... 60*71 ........ 51*6« 

6 H 6 .... 4-23 

2 8 82 .... 22-5S 22-74 

4 O 32 .... 22-53 

a»W90* 142 .... 100*00 

Aoeordiog to Wtthler, it ii Om^&O*. 

Bams, with evolution of ralpburous aoid. 

Dissolves yery readily in aUehol^ forming a deep yellowisb red 
solntion. 



Bromocarl)olic Acid. 

0»BrH»0» H 0«BrH»,0«. 

OAHons. (1045.) N. Ann, Ohim, Phys. 13, 103. 

MfomoegrboliUure, AM$ krcmepkinaiiqiii, 

. Obtained by distilling a mixture of bromosalioylio aoid, fine sand and 
a small qoantity of baryta^ and redistilling the distillate oyer si^nd and 
baryta. 

Coloarless liquid. 

Caboun. 

12 C 72 .... 41-61 .... 48'30 

Br 60 .... 46*24 .... 44-8d 

5H 6 ..„ 2-00 .,.. 8-57 

2 O 16 .... 9-25 .... 8-28 



.**» 



C"BrH»0» 173 .... JOO^OO .... 100-00 

As the bromosalicjlic acid used in the preparation was somewhat contaminated with 
saUcjlic add, the acid analysed contained also a certain quantity of carbolic addj hence 
too much C and H. (Cal^Qim.) 



SfXmine^udeui (?'Br"H*. 



Bibromooarbolic 

C»Br»H*0» = C"Br«H*,0«. 
CaBOUM {1845.) if. Ann. Chim. Phyt. 13, 103. 
Btbramearhoh^re, Aeide bromophinSnjue, 



HYDROBROMATK OP TBRBROMOBENZENE. 169 

Prepared like bromocarbolio aoid, exceptiDg that bibromosaliojlio acid 
18 nsed, and distilled tkree times over sand and baryta. 
Oil> which crystallises on cooling. (Cahours.) 



Terbromobenzene. C»Br»H». 

MiTSOHBRLiOH. (1835.) Pogg, 35, 374. 
Lassaionb. JRev. $cient 5, 360. 

Drihroa^wu, Brombenzidf Brombenziniie, IFunhnJ] 

PreparcUion. 1. Hydrobromate of terbromobenzene is distilled with 
hydrate of lime or baryta* (Mitscberlich,) — 2, The same compound is 
boiled with alcoholic potasn; the oil which is precipitated from the 
solution by water, dissoiTed in ether; the solution eyaporated; the residue 
cooled; and the resulting mass of needles pressed between paper, and puri- 
fied by reorystallisatioQ from ether. (Lassaigne.) 

• 

Properties. Oil having a powerful odour. (MitscherlicL) Silky 
needles, very fusible and distilling without deoomposition. (Lassaigna) 

Lassaigne. 

12 C 72 .... 22-86 ?5-92 

3 Br 240 .... 7619 

3 H 3 .... 0-95 1-05 

C»Bi»H* 315 10000 

Not deeonposed by distillation over hydrate of lime. (Mitscherlich.) 
Very easily soluble in alcohol and in Mer. (Lassaigne.) 



Hydrobromate of Terbromobenzene. 

CWBHH» -= 0"Br»H«,H»Br», 

LAMAiaKR it«v. teUni 5, 360. 

Jfy^iroAfOM* TVi^roN^MM^ BrombenMtn, Bronwre de Bengm$. 

Preparation* A mixture of benzene and bromine exposed to sunshine 
forms a solid compound. (Mitscherlich.) The powder thus produced in 
the course of l4days by exposure to the winter sun, is freed uom foreign 
matters by boiling with ether. (Lassaigne.) 

Properties. White inodorous and tasteless powder, which separates 
from its ethereal solution by eyaporation, in microscopic obliaue rhombic 
prisms, and after fusion, solidifies in ramifications made op or rhombs set 
one upon the other. (Lassaigne.) 



170 fiKNZ^NE : UUOMlNE-MUCLBUiS C^Bi^HK 



12 C 72 .... 12-90 130 

6 Br 480 ... 8602 

6H 6 .... 1-08 1-1 

C»Bi«H« 658 .... 100-00 

Dec&mpanttans. 1. When heated, it passes over partly as such (sub- 
limed, aocordiog to Lassai^ne), partly resolved into hjdrobromio acid, 
hydrogen, bromine and terbromobenzene. — 2. When heated with 
hydrate of lime, it gives off terbromobenzene. (Mitscherlich.) 

Comhinatums. It does not dissolve in water. (Mitscherlich. ) 
It dissolves sparingly in alcohol and in ether» (Lassaigne.) 



TerbFomocarboIic Acid. 

C»Br»HH)» = C»Br»H»,0». 

Laurent. (1841.) JV. Ann. Chim. Phys. 3, 211; also Ann. Phamu 
43, 212; also /. pr. Chem. 25, 415. — Rev, sdmt. 6, 74. 

DribroMearbolt&ure, BromophdMnoMrt, BromindcptentHure, Aeide bromom 
pMnitiquem 

Preparation, 1. Carbolic acid immersed in excess of bromine, 
becomes strongly heated, gives off hydrobromic acid, and solidifies on 
cooling, in a brown mass, which must be boiled with water and ammonia; 
the solution is subsequently filtered from a small quantity of brown matter 
and decomposed by hydrochloric acid; and the thick precipitate washed 
on a filter. (Laurent) — 2. Terbromosalicylic acid is distilled two or 
three times with fine sand and a small quantity of baryta. (Cahonra) 
—When indigo is decomposed by bromine-water and the product snbseqaently distilled, 
bromindoptene is obtained, together with a mixture (to be separated by potash) of bro- 
mindatmite (terbromaniline : Htifmann) which passes over, and bromindoptenic add 
(terbromocarbolic acid) which remains behind. (Erdmann.) 

Properties, Crystallises by fusion or sublimation, or from solutions^ 
in delicate white needles. Right rhombic prisms, having the acute lateral 
edges truncated; t : u =z 1X6°; u : u = 52,° and 128^ May be distilled 
without decomposition. Smells like terchlorooarbolic acid. (Laurent.) 

Laurent. Cahourt. 

12 C 72 .... 21 '24 22-55 .... 2265 

3 Br 240 .... 7316 71-40 .... 71-60 

3H 3 .... 0-S8 0-94 .... 1-19 

2 16 ... 4-72 5-11 .... 4-56 

C»Br»HW 331 .... 100-00 10000 .... 10000 

When boiled with nitric acid, it forms at first a reddish resin, which 
gradually disappears^ and on evaporation, crystals of picric acid are 
obtained. 



BUOMANIL. 



171 



The Terhromocai^lai-es or Bromophenuates, when heated to redness, 
generally leave a metallic bromide and give off terbromocarbolic acid [?]. 

The Ammonta'SaU crystallises in needles. 

Its solntion forms with concentrated chloride of barium or chloride 
of sirontiumj a precipitate composed of needles; with neutral acetate of 
leadf a white precipitate; with cupric acetate^ a red-brown precipitate 
soluble in alcohol; and with nitrate of HlveVj an orange-yellow precipitate. 

The acid dissolves in a^oAo^, but somewhat less than terchlorocarbolic 
acid. (Laurent.) 

SuMance isomeric %nth Terbromocarbolic acid, 

A concentrated aqueous solntion of salicylate of potash mixed with a small quantity 
of potash and then with a large quantity of brominei becomes heated and decolorised, 
gives off carbonic acid, and soon deposits a kermes-brown substance, which is insoluble 
in water, ammonia, cold potash, and alcohol, but dissolves with extreme facility in 
ether ; it contains, after washing and drying, 22*19 p. c. C, 71 '8 Br and 0*88 H ; and, 
when heated, gives off white vapours, which condense into delicate white needlet of 
terbromocarbolic acid. (Cahours, N, Ann. CAitn. Phyt, \Z, 43.) 



If. 0xyhr<min€^ucUu9 C«Bi*H*0». 

Bromanilic Acid. 

Ci»Br«HH)» = C'*Br»H»0»,0». 
Stenhovse. Phil, Mag, J, [4], 8^ 39. 

When bromanil is thrown into hot potash-ley, it immediately dissolves^ 
forming a deep purple solution which quickly deposits brownish red 
needles of bromanilate of potash; and on adding sulphuric or hydrochloric 
acid to an aqueous solution of this salt, or to a solution of bromanil in hot 
potash-ley^ the purple colour immediately disappears, and bromanilic acid 
IS gradually deposited^ in beautiful, shining, reddish crystalline scales, 
becoming bronze-coloured when diy. — The acid appears also to be formed 
by slow digestion of bromanil in water. 

Acid. Stenhonse. 

12 C 72 .... 2416 

2 Br 160 .... 53-69 5391 

. 2 H 2 .... 0-69 

SO 64 .... 21-46 

C»Br«H«0« 298 .... 100-00 

Poiaeh-8ali, Stenhouse. 

12 C 720 .... 18-35 

2 Br 1600 .... 40-77 40*87 

2 H 2-0 .... 0-51 

2K 78-4 .... 19-98 1978 

10 80-0 .... 20-39 

C»Br»K«0»+2Aq 3924 .... 10000 



The potash-salt dissolves readily in water, but is nearly insolable in 
alcohol. 



178 OXY-BROMINE-NUCLEUS CUfii^. 



Bromanilt 

Stbnhousb. PhU. Mag. J. [4], 8, 38. 

Formation and Preparation, Picric acid is digested with water and 
bromine for several hours in an apparatus in which the condensed vapours 
can flow back again, the bromine being also replaced as it evaporates. 
Bromaail is then produced together with bronopicrin and hjdrobromio 
acid c 

2C"X»H»0« + 28Br - C«Br*0< + 6C«XBi» + 6HBr. 
picric add. bromanil. bromopicrin. 

The small quantity of gas eTolred, incnasing somewhat towards the end of the opera- 
tion, contains no carbonic acid, but oonabts chiefly of nitrogen and its oxides, 
particularly nitric oxide, probably formed by decomposition of the bromopicrin.^ — 
On distilling the product, bromopicrin passes over, and bromanil remains 
together with nndecomposed picric acid. On dissolving out the latter 
with hot water, the bromanil remains in yellowish red crystalline scales 
contaminated with a small quantity of a reddish resinous substance, from 
which the bromanil may be freed by recrystallisation from alcohoL 

Properties. Golden-yellow crystalline scales, which melt into a 
brownish liquid when heated, and sublime in sulphur-yellow crystals. 

Stenhoose. 

12 C ...., 72 .... 16-98 17-16 

4 Br 320 .... 7547 7573 

4 o 32 .... 7-55 711 



C»Br*0* 424 .... 10000 10000 

Bromanil is converted by sulphurous acid into bromhvdranil. 
It is nearly insoluble in tpoter, slightly soluble in cold, but tolerably 
soluble in hot alcohol and ether. (Stenhouse.) 



BromhydraniL 

C"Br*H«0* = C?*Br*0«,H»0*. 



Stenhouse. Phil. Mag. J. [4], 8, 39. 



When sulphurous acid gas is passed through hot alcohol containing 
an excess of bromanil, the latter gradually dissolves, forming a colourless 



ClILOROBENZKNE. 173 

tolaiioHy which when snfficiently oonoentrated^ depoeiU bromhydraDil in 
oolonrleflB omtalB having a mother-of-pearl loatre. The compound 18 
also formed by boiling bromanil in aqneoos snlphurons acid, bat very 
dowlj, because both bromanil and bromhydranil are nearly insoluble in 
water. 

Bromhydranil^ when heated^ melts and readily sablimes^ forming soft 
eolonrless scales. 

StenhooBe. 

12 C 72 .... 16-90 17-U 

4 Br 320 .... 75-12 

2 H 2 .... 0-47 0'65 

4 O 82 .... 7-51 

C»Bi^HH>* 426 .... 100-00 

Bromhydranil is nearly insoluble in water, but dissolves abundantly 
in alcohol and ether. Ftom its concentrated alcoholic solution, it is pre- 
cipitated by water in the form of a white crystalline powder. 
(Stenhouse.) ^. 



Chlorine-nueleus C?»C1H» 

Chlorobenzene or Chloride of Phenyl. 
0"C1H» « c«H»,CL 

Laurent & Gbrhabbt. (1849.) Compt. (Mm, 1849^ 429: abstr. Ann. 

Pharm. 75, 79. 
Williamson & Scrughau. Cheni. SiwJ. Qu, J. 7, 238; Proe. Hoy, Soc, 
7,18. 

ChlorJwM, Chlorphenyl, 

Formation and Preparation. By decomposing carbolic acid with 
pentachloride of phosphorus, washing the resulting heavy oil with water 
and potash, and rectifjring. (Laurent & Gerhardt.) — % When 2 At 
pentachloride of phosphorus are added by small portions to 5 At carbolic 
aeid, a violent action takes place at first, great heat being developed and 
hydrochloric acid evolved : but this action soon ceases and it becomes 
necessary to heat the mixture. If it be then distilled upwards till it has 
nearly ceased to give off hydrochloric acid, and the distillate subsequently 
collected, about ) of the whole distils over below 240*^, and the tempe« 
rature then rapidly rises above the range of the mercurial thermometer. 
The distillate coflected below 240^ is a limpid colourless liauid, which 
when washed with hot water and subsequently with potasn, yields a 
thick oil which settles to the bottom of the vessel; ana on submitting 
this oil to fractional distillation, collecting apart the portion which passes 
over at 1 36^ to 1 38^ chloride of phenyl is obtained, nearly pure but in 
small quantity. The brown liquid which distils above the range of the 
thermometer is phosphate of phenyl, and constitutes by far the largest 
portion of the product. When an excess of chloride of phosphorus is 



174 BENZENE: CHLORINE-NUCLEUS C«C1H-. 

used in tlie preparation, the quantity of chloride of phenyl obtained 
appears to be still smaller than with the above proportions. (Williamson & 
Scrugham.) ^. 

Properties. Heavy oil, which, after washing with water and potash, 
and subsequent rectification, is destitute of odour. (Laurent & Gerhardt.^ 
Colourless^ mobile liquid, having a fragrant odour. Boih at 136^ (W. &S.) 

Laarent & Gerhardt Scnigham. 

12 720 .... 64-06 .... 67*2 66-58 

CI 35-4 .... 31-49 30-83 

5H 50 .... 4-45 .... 5-2 493 

C*^CIH» 112-4 .... 10000 102-34 

[The product examined by Laurent & Gerhardt was probably impure.] 

Decompositions. Distils at a somewhat high temperature, for the 
most part undecomposed. By water, and more quickly by aqueous 
potash it is converted into carbolic acid : C^*CIH» + KO + HO 
= C»H«0» -f- KCl. (Laurent A Gerhardt.) 



T CoT^ugated Compounds of Chlarobenzen^. 

Sulphite of Chlorobenzene. 

C»»CIH»S*0* = C"C1H»,2S0». f 
Obrhardt & Chancbi.. Oompt. rend. S5, 690. 

Chhrure phHyl^sulfttreux, Chhrure de suffophinyU. 

Obtained by distilling a sulphobenzolate with oxychloride of phos« 
phorus. Benxene is gently heated with an equal volume of oil of vitriol till 
It is completely dissolved, and a homogeneous red liquid obtained. Water 
is then added; the liquid saturated with chalk; the filtered solution of 
sulphobenzolate of lime mixed with a quantity of carbonate of soda just 
sufficient to precipitate all the lime; and the resulting solution of sulpho- 
benzolate of soda filtered aud evaporated to dryness. The soda-salt, after 
having been heated for some time in a stove to about 150% is introduced 
into a tubulated retort, and mixed with oxychloride of phosphorus to the 
consistenceof a thick paste, the materials being introduced in alternate small 
portions, because the action begins even at ordinary temperatures and is 
attended with considerable evolution of heat. The mixture is then dis- 
tilled as long as any oily liquid passes over, and the product rectified, the 
last portions which distil over at 254^, after the thennometer has become 
stationary, being collected apart as the pure product. The portion which 
distils over below 254* contains a considerable quantity of sulphite of chlorobenxene 
carried over with the vapours of oxychloride of phosphorus^ and may be used for the 
preparation of sulphite of amidobenzene. Sulphobenzolate of soda is better adapted 
than the lime-salt for the preparation of sulphite of chlorobensene, because it is 
more readily acted upon by the oxychloride of phosphorus. 



CHLOaOSULPJIOBENZOLlC ACID. 175 

Colourleas, strongly refractinar oil, of sp. gp. 1-378 at 23^ Fumes 
slightly in the air. Has a rather powerfal odour resembling that of 
bitter almonds. Boils constantly at 254°. 



12 C 


Calculation, 
72-0 


40-82 


5 H 


5-0 


2-83 


a 


35-4 


20-07 


2 8 


32-0 


18-14 


4 O 


32*0 . 


18-14 




C»C1H»SK>* 


176-4 


100-00 



Might alio be regarded as Ci2ClH'(S0^,H' or as chloride of solphobenzene 
CKH»S«0*,a. 

This^ compoand is bat little acted npon by water, which however 
renders it acid. The fixed alkalis decompose it immediately, forming 
an alkaline chloride and a snlphobenzolate : 

[C«aH»,2S0« + 2K0 = Ka + (?»H»K,2S0*.] 

Ammonia converts it into sulphite of anddobenzene, (or snlphophenyl* 
amide) and chloride of ammouiam : 

[C«aH»,2S0» + 2NH» - C>«AdH»,2S0» + NH*C1.] 

Snlphite of chlorobenzene is insoluble in water, but dissolves very 
readily in alcohol (Gerhurdt & Chancel.) 



Chlorosulphobenzolic Acid. 

C^C1H»S»0« = (7'C1H»,2S0»- 
L. HvTCHiNGs. Chem, Soc, Qu, J. z* 101. 

Sulphaie qf Chhrohenzene, Sulphate qf Pkenylic Chloride* 

Obtained by the action of fuming sulphnric acid on chlorobencene. 
The liquids gradually combine at ordinary temperatures; and on treating 
the mixture with excess of milk of lime, a soluble lime-salt is obtained 
which crystallises in microscopic tabular crystals. 

Lime*Malt. Hatchings. 

12 C 72-0 .... 34-03 

4 H 4-0 .... 1-92 

Ca 20-0 .... 9-46 9-26 

CI 35-4 .... 16-78 

2S 320 .... 15-13 15-22 

6 O 480 .... 22-68 

C»ClH<Ca,2S0« 211-4 .... 100-00 ^. 



176 BENZENE: CHLORINE-NUCLBUS C»«C1H«. 

Ghloroniceic Acid. 

C"C1HW == C»CIH»,0*. 

St. Etrk. (1849.) HT. Ann, Chim. Phy9. 25. 484; also Ann. Pharm. 
70> 257; alsoi «7. pr, Chem. 46, 449; Oompt rend. 25, 912. 

ChlomicetuSur€f Cklormcetniaurep Aeide nieAfUi numoehlorS, Aeide 
ehloronieiique. 

FomuUion and Preparation. Chlorine gas is passed for about two 
days ia the cold through a solotion of 1 pt bensoie lu^id And 83 pts. 
hydrate of potash^ by means of a tube widened at the end and thereby 
prevented from getting stopped up, till the liquid, which continually 
gires off carbonic acid gas^ first turns yellow, greenish yellow and 
fight green, then again yellow, and deposits a thick green crystalline 
magma of chloroniceate, chlorate, and a small quantity of bensoate of 
potash, above which there floats a solution of benzoate of potash 
and chloride of potassium. The entire mass is gently heated with 
iln eqtial Ijdantity of wateif; saturated with carbotiio acid; mixed with h 
small quantity of hydrochloric acid; heated to the boiling pointy whereby 
the whole of the saline matter is dissolved, and the chloroniceic acid 
separated in the form of a yellowish oil, which rises to the surface or 
sinks to the bottom and soon orystalKses; the watery liquid separated 
tberefrom; and the chloroniceic acid freed from admixed oenEoio aoio, partly 
by fusion under water, partly by repeated crystallisation from aJcohol 
or a mixture of ether and alcohol. From the benzoic acid obtained in 
this part of the process, as well as from the aqueous solution, an additional 
portion of chloroniceic acid may be prepared by fusion under water. 

Properties. Microscopic four-sided needles united in cauliflower-like 
masses; melts at 100% and in this state has a density of 1*29; bails at 
215% volatilising undecomposed, and subliming in flat needles, having a 
fatty lustre and united in stellate groups. In the melted itatOi it has a 
penetrating odour. 



12 C 


72*0 


.... 49-86 ... 
.... 24-51 .. 
.... 8*4/ •., 
.... 22-16 .. 


St. Erre. 
50-35 


CI 

5 H 


35-4 

50 


23-81 

3'36 


4 


32*0 


22-48 








C"C1H»0* 


144-4 


.... 100*00 .. 


100-00 



Decompositions. 1. Fuming nitric acid quickly dissolves chloroniceic 
acid, with violent action, and deposits crystals of nitrocMoroniceic acid, 
C»»C1XH*0*, while the mother-liquor retains the acid C^»C1XH*,0* — 
2. The mixture of the acid with fuming oil of vitriol forms a soluble baryta- 
salt, and therefore probably contains C"C1H»0*,2S0'. — 3. When the 
acid is distilled with excess of baryta or lime, a residue is left consisting 
of metallic chloride, alkaline carbonate and charcoal, while chloronicene^ 
C^^CIH^ passes over in the form of a brownish yellow distillate, and then 
paranicene C^H^% as a lemon-yellow sublimate. The acid is not acted 
upon by chlorine gas, even with the aid of heat, or by potassium- 
amalgam. 



CHLORONIC£AMID£. 177 

CombincUtans. The acid does not dissolve in water. 

CAlaronicecUe of AmrrMnia. — The acid dissolved in alcohol and satu- 
lated with ammonia^ yields broad micaceous laminsB, which are fusible 
and volatilise without decomposition. When exposed to light, they 
assume a brown colour and turn acid. 



12 C 

N 

CI 

8 H 


72-0 

14*0 

35-4 

8-0 


.... 44-61 .. 
.... 8-67 .. 
.... 21-93 
.... 4-96 .. 
.... 19-83 


St* Bvre. 

45-00 

8*90 

5*29 


4 O 


320 











C»C1H*(NH<)0< 161*4 .... 100-00 



CMcroniceate of Baryta. — White crystalline powder, which at a red 
heat, gives off the two hydrocarbons above mentioned, leayiu^ a carbo- 
naceous residue; dissolves sparingly in water and pretty easily in hot 
alcohol. 



12 


72*0 


.... tJO 90 .. 

.... 16*70 

.... X Oaf «.< 

.... 32-36 .., 
.... 1509 


St. Evre. 
33*78 


CI 

4 H 


35*4 

4-0 




Ba 

4 O 


68-6 

32-0 


32*83 








C^^ClH^BaO* 


212-0 


.... 10000 





CMoraniceate of Silver, -* The alcoholic ammonia-salt added to an 
alcoholic solution of nitrate of silver, throws down white flakes which^ 
after waahing, dry np to a soft crystalline powder, 

St. Eyre« 

12 C 720 .... 28-64 29*21 

CI 35-4 .... 14*08 

4 H 4-0 .... 1*59 205 

Ag 108*0 .... 42*96 43*21 

4 O 320 .... 12*73 

C^ClHUgO* 251*4 ... 10000 

The acid dissolves in alcohol. (St. Evre.) 



Ghloroniceamide. 

C"NC1H«0» = C"ClAdH*,0«. 

Amide ehloroniciique, Chloronieenamid, 

Obtained by placing an alcoholic solution of chloroniceic ether and 
ammonia together in a bottle for some time, and then evaporating to the 
crystallising point. 

Colourless laminsB having a hiij lustre and melting at 108^ 
(St Evre, If. Ann. Chim. Fhys. 25, 492.) 

TOL. XI. N 



178 BENZBNB: CHLORINE NUCLEUS C»«C1»H<. 

St. Etk. 

12 C 720 .... 50-21 50-51 

N 140 .... 9-76 9-58 

a 35-4 ;... 24-69 

6H 6-0 .... 4-18 4-27 

2 O 16-0 .... 1116 



C"NaH«0* 143-4 .... 10000 



Conjugatad Compound. 

Ghloroniceic Ether. 

C"C1H»0* = C*H»0,Ci*ClH*0«. 

Obtained by passing bjdrocblorio acid gas tbrough an alcobolic sola- 
tion of cbloroniceic acid, and rectifying the etber over litharge. 

Colonrless liquid, of sp. gr. 0-981, boiling at 230^ 

Its alcoholic solution is gradually converted bj ammonia into chloro- 
nioeamide : 

C"C1H*0* + NH» - CttNClHW + C*HW. 

(St. Eyre, N. Ann. Chim. Phys. 25, 491.) 



16 C 
d 
9H 
40 







8t. Btm. 


960 


.... 65*68 .. 


65-99 


35*4 


.... 20-54 .. 


20-23 


9-0 


.... 5-22 .. 


5-20 


320 


.... 18-56 .. 


18-58 



CWC1H»0* 172-4 .... 100-00 100-00 



CUorine^uOeuM C"CPH*. 

Biohlorocarbolio Acid. 

C"dl«HH)» = C»H31«H*,0*. 

Laurent. (1836.) Ann Chim Phys. 63, 27; also^n^i. Pharm. 23, 60; 
also J. pr. Chem. 10, 293. — Ann Chim. Phys. 3, 210; also Ann 
Pharm. 43, 212; also J. pr. Chem. 25, 414. 

BiehlorearhoMure, ChiorpMneiHImrB, AeM eJUorophMtipie. 

Formation. 1. By the comparatively feeble action of chlorine on 
carbolic acid. (Laurent.) — 2. By distilling bichlorosalicylie acid three 
times with fine sand and a small quantity of baryta or lime. (Cahours.) 

Preparation CoaUtar is distilled till the distillaie begins to exhibit 
a viscid consistence; chlorine gas passed through the yellowish oil for a 
day; the liquid then cooled to — 10^ and strained through linen to 
separate the naphthalin which has crystallised out; chlorine a^ain passed 
for two days through the liquid, which is then cooled to , decanUd 



BICHLOttOCARBOLtC ACID* 179 

from the crystallised hydrochlorate of bichloronaphtbaJiii ^C^C1*H',H'C1') 
and distilled (whereapoii it froths up considerably, giving off a large 
quantity of chlorine and afterwards hydrochloric acid) till the thick 
black residue exhibits considerable intumescence (quadrochloronaphthalin 
then subliming in needles); the distillate shaken up in a bottle with oil 
of vitriol as long as hydrochloric acid continues to escape; the rose- 
coloured oil of vitriol (which deposits a stinking substance when neatra* 
lized) removed by the syphon; the remainiog oil washed with a large 
quantity of water, and mixed in the flask with ammonia, with which it 
solidifies completely into a white mass^ with slight rise of temperature; 
this mass boiled with water; the solution decanted hot from a brown oil, 
which is again to be treated with ammonia and then with hot water to 
remove the acids eompletely; the hot-filtered aqueous solutions, con- 
taining bi- and ter-chlorocarbolate of ammonia, mixed by drops with 
dilute nitrie acid till a slight turbidity is produced; the liquid filtered 
from the red-brown precipitale; the filtrate precipitated with a slight 
excess of nitric acid; the white precipitate, which is gelatinous at first 
but afterwards curdy and consists of nne needles, collected on a filter, 
and distilled after washing, pressing and drying; and the distillate boiled 
with a slight excess of aqueous carbonate of soda, which leatres behind 
the oily bichlorocarbolic acid, whilst the crystalline terchlorocarbolio 
acid is precipitated from the filtrate by nitric acid, and purified by dis- 
tillation. (Laurent.) 

« 

Fropeiiies. 1. Oil, which volatilises without residue^ and has a 
peculiar odour. (Laurent) 



12 C 

' 2a 

4H 
20 







Laareni. 


72*0 


.... 44-23 ... 


41'49 


70-8 


..•■ 4o*4" ..1 


43-00 


AO 


.... 2-46 ... 


2-82 


16-0 


.... 9'82 ... 


12-69 



C«CPH*0* 162-8 .M. 100-00 ».i 100-00 

DeccmpadUons. 1. By the further iictloil of chlorine, the acid is con- 
verted, with evolution of hydrochloric acid, into terchlorocarbolio acid. 

C"CPH*0» + 2CI - Gi«Cl»H»0» + HCL 

2. Wheu boiled with nitric acid, it forms rery TolAtile nidedles. (Laurdtlt.) 

Comhinations. Insoluble in water. ... j* i 

When aqueous ammonia is poored upon the acid, it immediately 

solidifies into a crystalline mass, which however on exposure to the air, 

gives off ammonia and becomes oily, but solidifies when again treated 

with ammonia. The solid salt is soluble in water. 

The acid dissolvcfir with great facility in alcohol and in €iher. 

(Laurent.) 



yS 



180 BENZENK: CHLORINE-NUCLEUS C»Cl»Ha. 



Terchlorobenzene. 

MmoHBBUCH. Pogg. 35, 872. 

Laitbbnt. Ann. Chvm. Phy$. 68, 27; also Ann. Pharm. 23, 69. 

Driehiorfitne, CMorohenxid, ChloropkinUe. — Obienred by Faraday in 1825; 
more distiactly recognixed by Mitacherlich in 1833. 

Preparation. 1. By distilling a mixture of hydrocblorate of terchloro* 
benzene and excess of hydrate of lime or baryta. — 2. By distilling 
hydroehlorate of terchlorobenzene by itself in a tall flask, in whicb the 
portion that rises undecomposed can constantly run back again. (Mit- 
scherlich.) — 3. By boiling hydroehlorate of terchlorobenzene for some 
minutes with alcoholic potash, mixing with water, boiling the oil thereby 
precipitated with fresh alcoholic potash, precipitating again with water, 
drying over chloride of calcium, and rectifying. (Laurent.) 

PropeHies.. Colourless oil of sp. gr. 1*457 [at 7^ Boils at 210" 
Vapour-density 6*37. (Mitscherlich.) 

Mitacherlich. Laurent* 



12 C 


72'0 


.»•• Otl*7«S 

.... 58-62 

1-65 


••■t 


39-91 .... 
1-62 .... 


38*89 


3 CI 


106-2 




3 H 


3-0 


1-72 









C»a»H». 181-2 .... 100-00 

Vol. Density. 

C-Tapour 12 4*9920 

Cl-gag 3 7-3629 

H-gas 3 0-2079 

Vaponr of C»a»H«.... 2 12-5628 

1 6-2814 

Its vapour decomposes at a red heat. — Chlorine, bromine, acids and 
alkalis (even hydrate of lime and baryta when it is distilled with them) 
exert no decomposing action upon it. 

It is insoluble in water, but dissolves very easily in alcohol, ether, and 
benzene. 



Hydroehlorate of Terchlorobenzene. 

C"C1«H« = C»H}1«H«,H»C1». 

MiTSCHBRLiCH. (1835.) Poffff. 35, 370. 

Pelioot. Ann. Ckim. Phyt. 56, 66. 

Laurent. Ann. Chim. Phyt. 63, 27; also Ann. Pharm. 23, 68. 

Ilydroehlor m Trichiot:/kne, ChlorbenMtn, CMorobemone, Hydroehlorate (f« 
ChloropMkiie. 



TERCHLOROCARBOLIC ACID. 161 

F<mnaiiion» (p. 138). 

Preparation, When cUorine-gas is passed in sunshine into a capacious 
bottle containing a smsdl quantity of benzene, the chlorine is absorbed^ 
with rise of temperature and formation of white vapourJs; and crystals 
of hydrochlorate of terchlorobenzene shoot out from the benzene, which 
in the end is completely converted into the hydrochlorate. Nevertheless, 
a certain quantity of terchlorobenzene remains mixed with it, because 
the heat causes part of the hydrochloric acid to separate; on this account, 
the crystals must bo washed with a little ether (Mitscherlich), or purified 
by crystallisation from hot alcohol. (Peligot.) 

Properties. Transparent, colourless, shining laminie. (Peligoi) Right 
rhombic prisms with the acute lateral edges truncated. (Laurent.) Melts 
at 132®, and, if then gradually cooled, begins to solidify at 125"^, its tem« 
perature then rising a^ain to 132°. (Mitscherlich.) Melts at 135® to 
140° (Laurent); melts into an oil which begins to solidify at 50°. (Peligot.) 
Distils completely at 288°, but is at the same time partially decomposea 
into hydrochloric acid and terchlorobenzene. (Mitscherlich.) Boils at 
150®, and the distillate smells of chlorine and bitter almonds. (Peligot.) 



12 C 72-0 .... 24-79 

6 CI 212-4 .... 73-14 

6H 6-0 .... 2-07 

C»a«H« .... 290-4 .... 100-00 



It is resolved, partially when heated by itself, and completely when 
heated with hydrate of lime, into terchlorobenzene and hydrochloric acid 
r chloride of calcium. 

It is insoluble in water. (Mitscherlich; Peligot.) 
Dissolves sparingly in cold alcohol (Mitscherlisoh); readily in hot 
IcohoL (Peligot) 

Dissolves more abundantly in ether, and yields definite crystals when 
the ether evapoiate& (Mitscherlich.) 



MitscherUch. 


Peligot Laurent 


24-95 


.. 25-55 ,. 24-97 


2-02 


.. 2-33 2-28 



Terchlorocarbolic Acid. 
C«C1»H»0' = C»a»H>,0». 

Laurent. (1836.) Ann, Chim, Phys. 63, 27; also Ann. Pharm. 23, 60; 
also J^ pr. Chem, 10, 293. — iT. Ann. Chim. Phys. 3, 206; also 
Ann. Pharm. 43, 208; also J,pr. Chem. 25, 410. — iT. Ann. Chim. 
Phys. 3, 497. 

Erdmann. J. pr. Chem. 19, 332; 22, 276; 25, 472. 

PiRiA. N. Ann. Chim. Phys. 1 42, 269. 

Tyiekhrearbolsdure, Chiorphilnitsduref CMorindoptens^bwre, Acide chlwro* 
ph6Urique. 



188 BBKZBNB : CHL0R1NK-NUCLBU8 OK^fiB*. 

Formation, 1. By tho action of chlorine on carbolic or biduorocar* 
bolic acid TLanrent); or by the short action of chlorate of potash and 
hydrochlonc acid on carbolic acid. (Hofmann.) — 2. In the decomposi- 
tion of aniline by chlorine. (Hofmann.) — 3. Also of an aqaeous solution 
of saligenin. (Piria.) — 4. In the decomposition of indigo suspended in 
water by chlorine. 

Preparation* 1. Either by the method g^ven on pages 178, 179; or 
better: By repeatedly distilliuff the commercial oil obtained from coal-tar; 
collecting apart the portion which boils between 170 and lOO""; separating 
it out from the naphthaline which crystallises ont in the cold; passing 
chlorine-gas through it for a day or two according to the quantity; 
distilling it till nothing but a carbonaceous residue is left (whereby 
hydrochloric acid is giv^n off and a very offensire odour emitted), the 
receiver being changed at certain stages of the process, and the first and 
last portions of the distillate set aside; passing chlorine through the 
middle distillate till it solidifies into a crystalline paste; purifying this 
mass from adhering oil by spreading it on paper and pressing it; dis- 
solving the crystalline mass — which, besides the terchlorocarbolio acid, 
likewise contains a little oil and crystalline chloralbin (G^Gl'H*)— in 
boiling water containing ammonia; filtering; dissolving in water the ter- 
chlorocarbolate of ammonia which has crystallised out on cooling; mixing 
the solution with hydrochloric acid to precipitate the terchlorocarbolio 
acid; and purifying this product by washing, drying, and distillation. — 
(Laurent.) 

2. When chlorine gas is passed through an aqueous solution of sali- 
genin, the bottle being frequently closed and shaken^ the liquid imme- 
diately becomes turbid, then deposits a yellow, afterwards reddish and 
finally orange-yellow crystalline resin, and a white, bulky, crystalline 
precipitate. To free the entire precipitate from a closely adhering reddish 
oil, it is distilled three or four times with oil of vitriol, which cartionises 
the oil, with evolution of sulphurous and hydrochloric acid, and ulti- 
mately pure terchlorocarbolio acid distils over* (Piria.) 

3. By passing chlorine-ffas through water in which indigo is sus- 
pended, ana distilling the yellowish red magma, with cohobation of the 
watery distiUate, a small quantity of chlorindoptene is obtained sublimed 
in laminsB and needles. Now, when this mixture of terchlorpcarbolic 
acid and chlorindatmite (terchloraniline : Hoftruinn) is distilled with 
potash, the chlorindatmite passes over, while crystallised chlorindoptate 
of potash remains behind, mixed with free potash. This residue is 
pressed, exposed to the carbonic acid in the air, dissolved in the smallest 
possible quantity of boiling alcohol, and left to crystallise after filtration ; 
and from the aqueous solution of the capillary crystals thus obtained, the 
chlorindoptenic acid is precipitated by acids. (Erdmann.) 

Prqperties. Crystallises from solutions — best from rock-oil — or by 
sublimation, in white needles and prisms having a silky lustre. Right 
rhombic prisms with the acute lateral edges truncated; u : « = 70^ and 
110°; u: t= 145^. Melts at 44"^ to a colourless oil (at 5 8"* to a transparent 
oil of the colour of olive-oil : Piria; to a colourless oU : Hofmann), and 
on cooling solidifies in a radiated mass (translucent : Piria; exactly like 
stearic acid: Hofmann), Boils at 250° (at 156°: Piria), and volatilises 
tittdecompoeed; when kept for a year, it sublimes in needles even at 



TERCHLOROCA&BOUC ACID. 183 

ordinary iemperatnreB. Has a penetrating^ and very persistent disagree- 
able odour. (Laurent) Reddens litmus strongly. (Erdmann.) 

Laarent. Erdmann. Piria« 

JH9iUM. Earlier, JdUer. BarUer. Latir. 

12 C 72 .... 36-51 .... 3610 .... 3(i-98 .... 3802 .... 36-61 .... 35*91 

3 a 106-2 .... 53-85 .... 5000 .... 62-80 .... 5453 ^346 

3 H 30 .... 1-63 .... 1-89 .... 1*61 .... 1*77 .... 1-68 .... 1-84 

2 O 16-0 .... 8 11 .... 1201 .... 8-61 .... 5-68 8'79 

C«Cre»0«.... 197-2 .... 10000 .... 100-00 ... 100*00 .... 10000 10000 

BeeompofsUiont, 1. The acid is easily set on fire and bnrns with a 
green-edged smoky flame, emitting hydrochlorio aoid vapours. (Laurent.) 
— 2. Chlorine converts it into quintichlorocarbolic acid, but slowly and 
only when aided by heat. (Laurent.) — 3. With strong nitric aoid, it 
assumes a brown-red colour, froths up violently, and after continued 
boiling, yields, on cooling, golden-yellow inodorous scales which easily 
melt and sublime. (Laurent) — 4. Heated with chlorate of potash and 
hydrochloric acid, it is converted into chloranil. (Hofmann.) 

C»C1»H»0« + 4C1 + 20 » C^l*0* + 3HC1. 

Combinations. The aoid is insoluble in water (Laurent); nearly inso- 
luble in cold, sparingly insoluble in boiling water. (Piria.) 

It dissolves readily in warm fuming oil of vitriol and solidifies with 
it on cooling into a mass consisting of needles. (Laurent.) 

The TercTUoTocarholaJtn or Ckhropkenisates give off terchiorocarbolie 
aoid by dry distillation, leaving a metallic chloride and charcoal. They 
bum with a smoky, green-edged flame. Nitric acid added to these solu- 
tions, throws down the terchiorocarbolie acid in the form of a bulky 
mass. (Laurent) 

TerchloTOcarbolate of Ammonia. — The solution of the acid in aqueous 
ammonia, yields needles which have a slight alkaline reaction, and 
sublime completely when exposed to the heat of the sun, but by dry 
distillation in a retort, are partially resolved into nitrogen, ammonia, 
terchiorocarbolie acid, biehlorocarb<^ic acid, and sal-ammoniac. The salt 
dissolves very sparingly in cold, very easily in hot water, or in water 
containing alcohol. (Laurent.) 

Needhif dried in vacuo, Xjanrent. 



12 C 


72-e 


.... 33-62 .... 
.... 6-53 .... 
.... 49-58 .... 
.... 2-80 .... 
.... 7-47 .... 


.... 34*01 


N 

3 CI 


140 

106-2 


.... 7-20 
.... 49-83 


6 H 


e-0 


.... 2-50 


2 


16-0 


.... 616 









Ci2CPH«(NH<)0*.. 214-2 .... 10000 10000 

Terchlorocarbolate of Fotcuh, — Very soluble needles. (Erdmann.) 
TerchlorocarbolaU of Soda. — Very soluble needles having a silkj 
lustre. (Laurent) 

Terchlorocarbolate of Baryta, — The ammonia-salt precipitates chloride 
of barium only from somewhat concentrated solutions; — from cold solu- 
tions the salt separates as a jelly; but from hot solutions^ in long silky 



184 BENZENE : CHLORINE -NUCLEUS C»C1«H. 

needles. Tliese crystals, after diying in vacuo at 100°, contain 28*82 p.c 
baryta, and are therefore C**Cl'Ii*BaO'. When subjected to dry distil- 
lation, they give off the greater part of the acid undecomposed, but leave 
a residue of chloride of barium. They dissolve sparingly in water. 

The ammonia-salt throws down from concentrated (not from dilute) 
solutions of chloride of calcium, and likewise of alum, a white jelly; it 
precipitates neutral acetate of lead and ferrous salts, white; ferric salts, 
reddish (cdbaltous salts, reddish; nichel-sdUs, greenish, according to Erd- 
mann); cupric salts, brown-red Mark-purple violet, according to Erdmann 
and Hofmann^, the precipitate aissolving with brown colour in hot alcohol, 
and crystallising on cooling, in brown, shining, oblique rectangular prisms 
(mercurous nitrate, white, according to Erdmann); mercuric Maride, 
yellowish white; curdy; and nitrate of sUver, lemon-yellow. (Laurent) 

Erdmann, Laurent* 
SUver precipitate, at 120''. at 100% 

12 72-0 .... 23-67 .... 2493 

3 CI 106-2 .... 34-91 .... 35*32 

2H 2-0 .... 0-66 ... 0-95 

Ag 1080 .... 35-50 .... 36-36 .... 35*18 

2 O 16-0 .... 5-26 .. .. 2-44 

C»Cl»H«AgO* .... 304-2 .... 10000 .... 100*00 

The acid dissolves in woodr9pirit, and with extreme facility in alcohol 
and in ether; the alcoholic solution, on addition of water, deposits oily 
drops which gradually solidify; from the solution in hot, extremely dilute 
alcohol, the acid crystallises on cooling. (Laurent.) 

It dissolves very readily in oUs^ hoih fixed saia volatile. (Piria.) 



ClOorine^ucletu C»C1«H, 

Quinticlilorocarbolic Acid. 
C'KJPHO* = C»CPH,0». 

Erdmank. (1841.) J.pr, Chem. 22, 272. 
Laurbnt. iV^. Ann. Chim. Phys, 3, 497. 

QMmtieKlorcarboUHure, Chlorphdnuttthtre, geehlorte Chlonndoptentdure, Acid 
ehhrqphSntuique, 

Formation. By the action of chlorine on terchlorocarbolio acid dis- 
solved in heavy hydrochloric ether (viii. 373), or on chlorisatin or bichlo- 
risatm dissolved in alcohol. (Erdmann.) 

Preparation. Chlorisatin or bichlorisatin is treated with chlorine 

Ss m the manner described for the preparation ofchloranil (p. 195), and 
e resinous mixture which remains after obtaining the chloranil from the 
lower oily liquid and evaporating the oil (and if distilled, would yield 
long needles of chlorinated cblorindoptene [quintichJorocarbolic acid 
contammated with tercbloraniline] ), united with the perfectly similar 



CHLORKINONE. 185 

resinoas mixture precipitated by boiling tbe upper liquid with water. 
Both these mixtures are dissolved, with the aid of heat, in potash; the 
prisms of impure qnintichlorocarbolate of potash, which form on cooling, 
purified by recrystallisation from dilute potash, in which they are but 
sparingly soluble; and the acid separated in white flakes from the potash- 
salt by hydrochloric acid. (Erdmann.) — As Laurent, by nearly the same 
process, obtained brownish flakes, he boiled their solution in ammonia 
with a large quantity of water, till the excess of ammonia was expelled 
and a brown oil separated out; dissolved the laminas obtained on cooling 
(whereas the mother-liquor yielded needles of terchlorocarbolic acid) in 
water; precipitated them from the solution by hydrochloric acid; and 
finally purified the still somewhat coloured acid by distillation* 

Properties, Crystallises, best from rock-oil, in white right rhombic 
prisms truncated on the acute lateral edges, u :u about = 110°. Less 
fusible than terchlorocarbolic acid. (Laurent.) Also less volatile; but 
when distilled with water, it sublimes in the neck of the retort in long 
needles. Smells like terchlorocarbolic acid, but more agreeably. ^-» 
(Erdmann.) 









jMumU 


12 C 


It... /a 


,.M 27*07 .. 


27-8 


5 CI 


.... 177 


.... 66*54 


65-7 


H 


■.... L 


.... 0-37 .. 


0-6 


2 


16 


6-02 .. 


5*9 


CW01*HO» ... 


..... 266 


.... 100-00 .. 


100-0 



QuirUicMorocarbolaie of Ammonia. — Aggregated needles very 
sparingly soluble in water. (Laurent.) 

QuintiMorooarbolate of Potash, — Rhombic prisms and needles; 
(Erdmann.) 

The potash-salt does not precipitate the salts of lime or magnesia; 
it precipitates chloride of hanum in white flakes; neiatrU acetate of lead^ 
white ifeiTOUs and/<!mc salts, brownish white; nitrate of cobaU, reddish; 
nitrate of nichd, greenish; cupric sulphate^ dark purple violet; m^'curous 
nitrate, in white flakes; mercuric chloride, in yellowish white flakes; 
nitrate of sU^fer^ lemon-yellow. (Erdmann.) 

SiiPerpreeipUate. Erdmann (at 110^)* 

12 C 72 .... 19*41 20-10 

5 CI 177 .... 47-71 46-81 

Ag M.... 108 .... 28-57 31'4l 

2 O 16 .... 4-31 1-68 



C»Cl»AgO* 373 .... 10000 100-00 

Oxychlorine-nudeus C^CIH'O*. 

Chlorkmone. 
C"C1H»0* = C"C1H*0*,0*. 

Stadler. (1849.) Ann. Pharm. 69, 300, 
Quinone monocMorie, 



1S6 BENZENB : OXYCHLORINB-NUCLEUS OuaH«0>. 

Preparation, 1 pt of kinate of copper or any other klnate (25 
gramriies at most) is distilled with 4 pts. of a mixture of 3 pts. common salt^ 
§ pts. peroxide of manganese, and 4 pts. oil of vitriol (diluted with 
8 times its bulk of water), in a flask provided with a descending tube 6 ft 
long, and kept cool at the upper part bj a wet doth, but not so much 
as to cause the liquid which distils over to crystallise. At first the 
mixture froths up considerably, giving off carbonic acid with a small 
quantity of chlorine, but when the liquid begins to boil, the evolution of 
chlorine ceases; the rapid ebullition is kept up, as long as any oil passes 
into the receiver from the tube, in which, if it be moderately cooled, all 
jthe cfaloranil is deposited. This oil, which solidifies on cooling, is 
collected on a filter, repeatedly washed with cold water, dried, pulverised 
and exhausted with successive small quantities of cold 85 p. c. alcohol, 
ad long aa the alcohol acquires a yellow colour and ffives a precipitate 
with water. Bichlorkinone then rpmains undissolved, together with a 
^mall quantity of terchlorkinone and chloranil, whilst the alcohol retains 
in solution the kinone and terchlorkinone, which colour it yellow. These 
compounds are precipitated from the solution, by addition of a treble 
volume of water, in slender needles and laminsB, and dissolved in a 
small quantity of hot, moderately strong alcohol; the solution cooled, till 
the large yellow laminsd of terchlorkinone which separate out, begin to 
he associated with needles of chlorkinone; the liquid then immediately 
filtered and mixed with water; and the precipitate consisting of chlor- 
kinone and a small quantity of terchlorkinone, freed from the latter 'by 
repeatedly treating it as above with alcohol, which however cannot be 
effected completely and is attended with great loss. 

Properties. Very soft yellow needles, which melt at 1 00**, forming a 
dark yellow oil having a peculiar aromatic odour and sharp burning 
taste; its solution imparts a purple colour to the skin and other organic 
substances. Neutral. 

St&deler. 

12 C 72-0 .... 50-56 3948 

CI 35-4 .... 24-86 41-31 

3 H 30 .... 2-11 1-15 

4 320 .... 22-47 1806 

/' C^aClHK)* .... 142-4 .... 10000 10000 

The above analysis gives nearly the formula of bichlorkinone or of a compound of 
chlorkinone and terchlorkinone in equal numbers of atoms ; but the lamins which 
occurred so abundantly in the substance analysed, showed clearly that it was a mere 
mixture of cBlSfkinohe and terchlorkinone. 

Decompoaitions. 1. The aqueous solution when boiled, becomes dark 
red and opaque, with formation of brown chlorkinhydrone (C^Cl'H^O*) 
and a brown resin. — 2. The reddish yellow sc^ution in cold oil of vitriol 
quickly solidifies into a magma of white needlea — 3. Chlorkinone 
dissolves very readily in cold aqueous sulphurous acid, as chlorhy- 
drokinone : 

C«CIH»0*-+ 2SO» + 2HO « C'»C1H»0* +. 2S0». 

Conihinations, Chlorkinone dissolves in boiling K^a^^ and separates 
on cooling. 



CHLORHTBROKINOMB* 187 

It dissolyes in ether and in strong cdeohol. Also in a hot mixture of 
strong alcohol with an equal qnantitj of water; but on cooling, part of 
it separates ont, and the portion which remains dissolved, changes the 
yellow colour of the solution by deoomposition.into wine-red. 

With strong and weak acetic acid, it behayes in the same manner as 
with strong and weak alcohoL (Stadeler.) 



Chlorhydrokinone. 

C'»C1H»0* = C"C1H»0»,H«0«. 

WoHLER. (1845.) Ann. Pharm. 51, 155. 
Stadelbb. Ann. Pharm. 69, 306. 

Colourlen Chlorhydrokinone, Hydroquinone monochlor^. 

Formaiian and Preparation. 1. The solution of kinone in strong 
hydrochloric acid, after it has become colourless, Is evaporated till it 
crystallises. The brown colour which the solution sometimes acquires 
during the evaporation, is likewise imparted to the crystals. (Wohler.) — 
2. By dissolving chlorkinone in aqueous sulphurous acid. Since however 
chlorkinone, as hitherto obtained, always contains terchlorkinone, the 
process likewise yields terchlorhydrokinone. (Sl^deler.) 

Properties. Colourless needles united in radiated groups, which melt 
very easily and solidify in the crystalline form on cooIIds;; sublime at a 
somewhat stronger heat, in shining laminsB, and with partisJ carbonisation; 
have a fednt peculiar odour, and sweetish, burning taste. 

WOhler. Schnedermann. 

12 C 720 .... 49-87 ^ 50-21 .... 50-42 

CI 35-4 .... 24-51 24-31 .... 23'82 

5 H 50 .... 3-46 3-61 .... 3*60 

4 32-0 .... 2216 21-87 .... 22-16 



C«aH»0* 144-4 .... 100-00 100*00 .... 100-00 

Decompositions. 1. Its aqueous solution immediately reduces silver 
from the solution of the nitrate, in specula and spaugles, with emission 

of the odour of kinone (pr of chlorkinone ? according to the following equation : 
CWCIH*0* + 2(AgO,NO») « C»«C1H»0* + 2Ag + 2H0 + 2NO»). (Laurent.)— 
2. The aqueous solution mixed with sesquichloride of iron, assumes a 
dark brown-red colour, becomes milky, and deposits dark brown oil- 
drops, which soon change to blackish green prisms (2C*2C1H*0'» + 2C1 
= C»*CPB80* + 2HC1. Laurent, Compt. Chim. 1849, 190.) — 3. The deep blue 
-solution of chlorhydrokinone in ammonia quickly turns green, then 
yellow, and lastly brown-red. (Wohler.) 

Combirtotions. It dissolves very readily in tvateTj alcoliol and ether, 
in the vapour of which it deliquesces. (Wohler.) 



188 BENZENE: OXYCHLORINE -NUCLEUS C«CPH«0*. 



Conjugated CompoutuL 

Chorkinliydrone. 

C«CI»H»0* = C*H:!lH•O^C"ClHW. 

Stadeleb. Ann, Pharm. 69, 307. 
Broum Chlorhydrokinone. 

FomuUion, 1. Bj digesting aqueous chlorhydrokiJione with chlor- 
kinone : 

C»C1H»0* + CMCIHW « (?*a2H«08. 

2. By mixing aqueous chlorhydrokinone with sesquichloride of iron; as 
shown hy W5hler (jmp,) — 3. By continued boiling of chlorkinone with 
a small quantity of water, (p. 186.) — 4. By the first action of strong 
hydrochloric acid upon kinone. (p. 160.) 

Chlorkinhydrone Is an oil^ which, after some time, solidifies into a 
greenish brown crystalline mass : and this, when kept (in a sealed tube) 
sublimes in delicate brown needles, which impart a deep purple colour 
to the skin ; it is decolorised by oil of vitriol, and appears therefore to 
contain water. 

It reddens litmus, and forms a white precipitate with an alcoholic 
solution of neutral acetate of lead. (Stadeler.) 



O^chlorine^ucUus C*»CPH*0». 

Bichlorkinone. 

C»C1»HW = C»C1»H*0«,0». 

Stadeleb. (1849.) Ann, Fharm, 69, 309. 

Preparation, From the mass obtained by distilling a salt of kinio 
acid with a chlorine-mixture, (p. 186) the chlorkinone and the greater 
part of the terchlorkinone are extracted by cold alcohol, then the rest of 
the terchlorkinone by hot alcohol mixed with an equal rolume of water; 
the remaining mixture of bichlorkinone and a small quantity of chloranil 
dissolved in hot alcohol; and the crystals of bichlorkinone, after cooling, 
freed by elutriation of the mother-liquor from the delicate needles of chlo^ 
ranil, and purified by crystallisation from a mixture of ether and alcohol. 

PropeHm, Dark yellow (lemon-yellow when crystallised from 
alcohol alone) glassy, oblique rhombic prisms, having their terminal 
faces obliquely set upon the obtuse lateral edges. Melts at 150°, becomes 
each time darker in colour, and volatilises slightly on exposure to the 



BICHLORHYDROKINONE. 1 89 

air^ more when boiled with water. Has a faint aromatic odour and is 
nearly tasteless. Its solution is neutral and does not colour the skin. 

Stttdder. 

12 C 72*0 .... 40-73 ..„ 40-72 

2 CI 70-8 .... 40-04 .... 40-14 

2H 20 .... 113 .... 115 

4 320 .... 1810 .... 17»9 

C'^CPH'O* 176-8 .... 10000 .... 10000 

Dec$mpodtions, Its deep red-brown solution in weak potash, deposits, 
after a few hours, slender red prisms of a potash-salt, from whose wine- 
red aqueous solution, hydrochloric acid throws down an acid (not further 
examined) resembling chloranilic acid and likewise forming red prisms. 
It dissolves sparingly in ammonia, forming a yellow solution which 
changes to red and then to black-brown; and if then evaporated, leaves 
sal-ammoniac and a brown substance, which yields a copious brown preci- 
pitate with hydrochloric acid. — When it is boiled with water, part of it 
volatilises undecomposed, and the remaining portion colours the water 
violet by decomposition. — By boiling with aqueous sulphurous acid, 
bichlorkmone is converted into bichlorkinhydrone and bichlorhydro« 
kinone : 



and; 



2CMCPH«0* + 2S03 + 2H0 - C«C1<H<08 + 2S0»j 
C"a«H«0* + 2S0a + 2H0 = C^CPH^O* + 2S0>» 



CambinoHons, Bichlorkinone is insoluble in water. 

It dissoves in oil of vitriol without decomposition, forming a yellow 
solution from which it crystallises as it gradually absorbs water. 

It difisolves without decomposition in strong boiling hydi'ocfdoric acid, 
and crystallises out on cooling. 

It dissolves sparingly in cold, abundantly in hot nitrie acid of sp. gr. 
1*25, forming a yellow solution from which it crystallises undecomposed 
on cooling. 

It dissolves readily and with yellow colour in ether. 

It is nearly insoluble in cold strong alcohol, but dissolves abundantly 
in the same liquid at the boiling heat, forming a yellow solution from 
which it separates for the most part on cooling; the mother-liquor, after a 
few days, assumes, a dark brownish green colour, and then on addition of 
water becomes red. In spirit of 40 per cent, it dissolves but very 
sparingly, even on boiling. 

It dissolves pretty freely in strong boiling acetic acid, separates there* 
from on cooling in long pnsms, and leaves a mother-liquor which soon 
becomes brown-red by decomposition. (Stadeler,) 



Bichlorhydrokinone. 

C»C1«H*0* = C«Ca*HH)»,H«0». 



Stadbleb. (1849.) Ann. Pharm. 09, 312. 
Colourlea BkhhrhydroMnwM^ 



190 BENZENE : 0XYCHL0RINE-NUCLBU8 C^Cim^Oi. 

The colourless solaiion (vid. t«^.) obtained by heating biohlorkinone 
with concentrated solphnrons aoid, deposits on eoolingy prisms which 
mast be washed with cold water and dried. 

Colourless needles and shorter prisms, resembling oxalic acid^ having 
a pearly lastre, and united in stellate groups. Melts at 105^, forming a 
red-brown liquid, which solidifies again without colour on cooling. 
Sublimes at 120^ in delicate needles, at 160°, yerj quickly, and when 
heated in contact with the air, diffuses white aromatic Tapoars. Has a 
burning aromatic taste. Reddens litmus. 

Stadder. 

12 C r2-0 .... 49-27 ; 40*24 

2 CI 70-8 .... 39-60 

4 H 4*0 .... 2-24 2-25 

4 32-0 .... 17-89 

C»CPHK)< 178-8 .... 100-00 

DecampoHtioM. I* When set on fire, it bums with a very bright, 
green-edged flame. — 2. When immersed in nitric acid, it is immediately 
couTerted into biohlorkinone. Similarly, when its hot aqueous solution 
is mixed with a suflicient quantity of sesquichloride of iron^ whereas a 
smfdler quantity throws down riolet or greenish black crystals of hydrated 
bichlorkinhydrone. [C^l*H*0*-|-4Aq!j Its solution in w€»k alcohol 
added to a neutral solution of nitrate of silver, precipitates, slowly at 
ordinary temperatures, more quickly at the boiling hea^ a silver 
specnlam, and yellow anhydrous, together with violet hydrated bichlor- 
kinhydrone, but it does not part with a greater quantity of hydrogen.— 
3. Its colourless solution in weak potash turns green and afterwards red 
on exposure to the air, and soon deposits a violet powder. — 4. Its yellow 
solution in ammonia becomes deep red on exposure to the air, and then 
jrields a brownish deposit containing a crystalline and an amorphous 
substance. 

ComhinatioM. It dissolves very sparingly in cold^ readily in hot 

W€lt6f» 

It is insoluble in cold, but dissolves in warm ail of vitriol, and crys- 
tallises therefrom on cooling, especially if the oil of vitriol can abstract 
water from it. 

It dissolves sparingly in boUing hydtocKlorie acid, and separates on 

cooling. 

It dissolves in ammonia with yellow colour, and in p&taA without 

colour. 

It forms a white precipitate with neutral lead-acetate dissolved in 
alcohoL 

It dissolves very readily in alcokot, eiher, and warm acdie acidi 



Chloranilic Acid. 

C^"CPH«0" = C^»C1«H•0^0^ 

Erdmakn. (1841.) J. pr. Chem. 22, 281. 

Formation and Preparation. The purple solution of chloranil in 
warm dilute potash (p. 197), deposits on cooling, nearly all the chlorani* 



CHLORANILIC ACID. 191 

late of potash that has formed in it; this salt is then separated from the 
nearly decolorised mother-liquor (containing chloride of potassium and 
potash), and purified by recrystallisation from water. The cold aqueoncf 
solution of these crystals assumes a reddish yellow colour on addition of 
hydrochloric or sulphuric (not of acetic) acia; and soon afterwards depo- 
sits the chloranilio acid in reddish- white, micaceous scales, which, when 
collected on a filter, exhibit the colour of red lead. When the aqueous 
solution of chloranilate of potash is heated with an excess of the preci- 
pitating acidy the chloranilio acid is deposited on eooling in granules and 
laminad. 

Properties. Minium-coloured scales, granules or laminae, which 
sublime but partially when heated in a test-tube, the greater part turning 
brown and decomposing. 

At 120*'. Erdmaxm. 

12 C 72-0 .... 34-48 .... 35-08 

2 CI 70-8 .... 33-91 .... 3348 

2H 2-0 .... 0-96 .... 1-05 

8 64-0 .... 30-65 .... 30-39 

CMCPH«08 208-8 .... 100-00 .... 100-00 

Decompoivtion. The violet i^olution of the acid in water is decolorised^ 
by nitric acid, with erolntioii bf a colourless gas; 

ComhinaiioiM, The crystallised acid contains 7*14 p. b. (2 At.) 
water, which escape at 120 . — It dissolyes with yiolet colour in water, 
and is precipitated therefrom by hydrochloric or sulphilric acid, with 
decoloration of the water. 

Chloranilate of Ammonia. — The solution of the acid in warm 
ammonia yields crystals on cooling, which resemble the pbtaeh-salt in^ 
i^pearance and in their chemical relations. 

Chloranilate of Potash, — Preparation a» above. Brownish purple prisms 
having a strong lustre. They do not ^ve off water at 100°, but bum at 
a higher temperature, with slight detonation and emission of purple 
vapours. (In dilute hydrochloric acid, they assume a red-lead colour 
without alteration of form : Hofmann,) They dissolve to a moderate 
amount in water and alcohol, forming violet-purple solutions; and to a 
smaller amount in aqueous potash. 

Cryttals, Erdmaxm. 

12 C 72-0 .... 23-75 24-06 

2 CI ;... 70-8 .... 23-35 

2 H 2-0 .... 0-66 ...;.... 0-89 

2IL0 94-4 .... 81-13 ......;. 80-77 

8 O 64-0 .... 21-11 

C»C1»K«0« + 2Aq .... 3032 .... 100-00 

The aqueous solution of the potash-salt precipitates cA/pru£«o/Wmm 
in red-brown micaceous scales very sparingly soluble in boiling- water; — 
with neutral acetate of lead it forms a brown precipitate; — with ferric 
nitrate, blackish; — with cwprtc sulphate, greenish brown; — with m^r- 
curous nitrate, yellowish brown ; and with nitrate of «7v«", a red-brown 



192 BENZENE: OXYCHLORINE-NUCLEUS C^^cuHSQ). 

pnWeralent precipitate, which dissolves very sparingly and with reddish 
colour in water. It does not precipitate the protosalts of iron, oohalt or 
nickel, or corrosive sublimate. (Erdmann.) 

SUver-preeijniaie, Erdmann* 

12 C 72-0 .... 17-03 17-40 

2 CI 70-8 .... 16-74 16*64 

2Ag 216-0 .... 51-09 51-06 

8 64-0 .... 1514 14-90 

C^CPAgW 422-8 .... 10000 10000 



Bichlorkiiihydrone. 

C«*C1*H»0« = C1"CHK)*,C>>C1«HK>*. 

Stadelbr. (1849.) Ann. Pkarm. 69, 814. 
Cdkiured BieMcrhydrokinone, 

Obtained in the hydrated state by digesting aq^neons bichlorhydro* 
kinone with bichlorkinone, or with the proper quantity of sesquichforide 
of iron (if too little is used, bichlorhydrokinone remains unaltered; and 
with too much, bichlorkinone is formed), washing with cold water the 
crystals produced from the brown mixture on cooling, and drying them. 
These crystals may be freed from water at 70° or aSove, without losing 
their form. 

Properties. Crystalline, yellow in the cold, becoming red every time 
it is heated above ] 10^ Has a faint odour like that of bichlorkinone, 
and an aromatic burning taste. 

Stitdeler. 

24 C 144-0 .... 40-50 40-59 

4 CI 141-6 .... 39-82 

6 H 6-0 .... 1-69 1-91 

8 64-0 .... 17-99 

C»*C1«H«0» 356-6 .... 100-00 

DeeompoaUions. 1. Bichlorkinhydrone melts to a red liquid at 120°, 
and at the same time sublimes in isolated crystals of bichlorkinone and 
bichlorhydrokinone. — 2. It is not altered by cold dilute nitric acid, but 
moderately strong nitric acid converts it into bichlorkinone. — 3. Its 
solutions are turned green by hypochlorite of soda. — 4. Its chrome- 
green solution in dilute potash quickly changes to ruby-red, but is then 
no longer precipitated by hydrochloric acid; whereas the ammoniacal 
solution, which, in other respects, behaves in the same manner, forms 
with hydrochloric acid, a pale cochineal-coloured precipitate. 

Comhinations. HydrcUed Bichlorhinhydrone. Preparation, vid. mp.-^ 
Ordinarily, small dark violet prisms united in stars; but when prepared 



TERCllLOKltINOK£. 193 

1>y mixing a Lot aqueous solation of bichlorhydrokinone with sesqui- 
chloride of iroo^ it forms long flat blackish green needles like kin^ 
hjdrone. The crystals, placed over oil of vitriol, or heated to 70°, give 
off their water, without change of form, and leaves the anhydrous yellow 
compound. Under oil of vitriol or a small quantity of alcohol, they also 
give off water and turn yellow. 

Stadeler. 

24 C 144-0 .... 36-77 36*90 

4 CI 141-6 .... 36-16 

10 H 100 .... 2-55 2-75 

12 O 96-0 .... 24-52 



C»^Cl^H«08 + 4Aq .... 391-6 .... 100-00 



Or: 



StUdeler. 

C2<C1^H«08 355-6 .... 90-81 90-91 

4 HO 36-0 .... 9-19 9-09 

391-6 .... 10000 10000 

Bichlorkinhydrone is scarcely soluble in cold wcUer, bat dissolves 
readily in boiling water, whence it separates on cooling, partly as the 
yellow anhydrous compound, partly as the violet hydrate. 

It dissolves with yellow colour in oil of vitriol, and crystallises out, 
also with yellow colour, as the oil of vitriol gradually takes up water. 

It dissolves with chrome-green colour in aqneoos ammonia or potash. 

It dissolves readily and with yellow colour in alcohol. 

It dissolves very readily in ether. The solution yields by spontaneous 
evaporation, partly yellow, partly violet crystals. 

^rom the deep red solution in hot strong acetic acid^ it crystallises on 
cooling in thin dark green prisms. (Stadeler.) 



OxycUorine-nuclew C^^d'HO*. 

Terchlorkinone. 

C^'Cl'HO* = C'>CPHO»,Ol 

WosKRESSENSKT. (1839.) J. p7\ Chem, 18, 419. 
Stadeler. Ann. Fkarm, 69, 31 8. 

Triehlorehinon» 

Formation, By the action of chlorine upon kinone. 

Preparation, 1. Dry chlorine gas is made to act upon kinone, which, 
in order that the temperature may not rise too high, must not be in large 
quantity, and must at first be cooled from without, but afterwards, to 
complete the decomposition, must be surrounded with hot water; the 

VOL. XI. ^ 



] 94 BENZENE ; OtTCHLORINE-NUCLBUS Ci^CPHO^. 

resulting terehlorkinone, partly carried forward by the oblorine-gas, nnd 
partly Bublitned in yellowish laminie in the receiver, is then purified by 
eolation in boiling alcohol and crystallisation, after addition of a small 
quantity of cold water. (Woskressensky.) —2. It is obtained in the pre- 
paration of chlorkinoue (p. 186), and freed from that compound by 
repeated solution in hot moderately strong alcohol; as the solution cools, 
the terchlorkinone crystallises out first, and may then be washed with 
cold alcohol. The portion of terchlorkinone which dissolves together 
with the chlorkinoue is precipitated by water, and further purified by 
alcohol, as above. (Stadeler.) 

PropertieB, Large golden-yellow laminss. (Stadeler.) Pale yellow, 
soft to the touch, friable. (Woskressensky.) Melts at 160° (somewhat 
above 100°, according to Woskressensky); and sublimes at 130° in deli- 
cate yellow iridescent lamina?. (Stadeler.) Has a penetrating aromatic 
odour (Woskressensky); nearly inodorous, and at first tasteless, but after- 
wards produces an unpleasant scratching sensation in the throat 
(Stadeler.) The alcoholic solution does not redden litmus (Woskres- 
sensky), or colour the skin or other organic tissues, unless it contains a 
small quantity of chlorkinoue, in which case it reddens them (Stadeler); 
•it imparts a <lark red colour to organic subatancea. (Woekreeaensky.) 

Wdkressensky. StSdekr. 

12 C 72-0 .... 34-09 34-11 3448 

3 a 106-2 .... 60-29 4945 50-10 

H 10 .... 0-47 0-79 0-54 

4 O 32-0 .... 1515 15-65 14-88 

C«CPHO* 211*2 .... 10000 10000 100*00 

Decompodtiofu, 1. When immersed in dilute potash, it turns green^ 
then dissolves with red-brown colour, and after a few hours, deposits 
long red needles of a potash-salt, from whose wine-red aqueous solution, 
hydrochloric acid throws down red needles of the peculiar acid mentioned 
at page 189. (Stadeler.) •— 2. W^ith ammoniacal gas it forms emerald- 
green crystals. (Woskressensky.) It dissolves after a while in weak 
ammonia, forming a red solution; with strong ammonia, it produces at 
first a green colour, but afterwards forms a brown-red solution, which 
when left to evaporate, forms small, hard, dark brown crystals. (Stadeler.) 
— 3. By hot aqueous sulphurous acid, it is converted into terchlorhy- 
drokinone. (Stadeler.) 

Combinations, It is soluble in cold, but dissolves very sparingly in 
boiling water. (Stadeler.) 

From its deep yellow solution in cold oil of vitriol, it is precipitated 
by water. (Stadeler.) 

From its solution in hot strong nitric acid, it crystallises in yellow 
JaminsB on cooling. (Stadeler.) 

Its alcoholic solutiou does not precipitate netUral acetate of lead or 
nitrate of silver, (Woskressensky.) 

It dissolves sparingly in cold, more abundantly in hot dloohcl, and 
aeparatea on cooling, the more completely aa the alcohol ia weaker. 
(St&deler.) 



tEHCHLORHYDROKINONE. 195 

It diBsolves in etker, (Wofikressensky, Stadeler.) 
With acetic acid, both strong and weak^ it behares as with alcohol. 
(Stadeler.) 



Tdroblorhydrokinone. 

C"C1»H»0* = C**CPHO»,H«0». 

StIdjelbr. (1849.) Ann. Pharm. 69^ 321. 

Preparation, The colourless solution of terchlorkinono in a suffident 
<|ii&fititj of hot aqueous sulphurous acid, deposits the terchlorhjdroki* 
none, on cooliug, in small crystalsi or on evaporation oTer the water- 
bath in the form of a heavy oil which crystallises as it cools; a portion, 
however, remains in solution, and may be obtained by evaporating the 
aqueous solution in vacuo over oil of vitriol. It is freed from adhering 
sulphuric acid by washing with cold water. 

Properties. Colourless laminie and flat prisms, which melt somewhat 
above 180°, and sublime in delicate iridescent laminsa. Has a faint 
aromatic odour, and a burning aromatic taste, especially when moistened 
with alcohol The alcoholic solution reddens litmus. 

DecomposUioTU. 1. Its solutions are coloured green by hypocMorUe 
of $oda. — 2. Strong (not dilute) nitric acid, converts it by oxidation 
into terchlorkinhydrone. The same compound appears to be fenned on 
adding nitrate of silver to a weak alcoholic solution of terchloffaydrokK 
none, a specular deposit of silver being formed after some minutes (or more 
quickly if aided by heat), and afterwards yellow rhombic lamina depo- 
mted,-— or when to the same solution, sesquvcfitoride of iron is added, 
which at first produces a deep brown colour. •— 3. Its solution in aqueocn 
potash or ammonia, which is colourless at first, turns green, red, and brown 
when exposed to the air, and afterwards, without depositing crystals^ 
forms with hydrochloric acid a thick precipitate, which, when formed 
from the potash-solution, is converted by boiling into a heavy mixture of 
light yellow laminse and black-blue crystals recognisable by the micro^ 
fioope, and when formed from the ammonia-salt appears nesh-coloored 
and amoTphoua 

Com&inations. It dissolves sparingly in cold tpoter, slowly and with 
fusion in boilinc^ water, from which it separates partially on cooling. 

From its solution in warm oil of vitriol, it crystallises as die liquid 
absorbs water. 

Its alcoholic solution forms a white precipitate with neiUrcU acetate of 
lead. 

It dissolves readily in alcohol and ether. 



2 



196 SENZeKE : CHLORtSE-NUCLEtS C»*CHO«. 



Conjugated Compound. 

Terchlorkinhydrone. 

C>*C1W0« = Ci«Cl»HO*,C*»Cl»H*0*. 

Stadblbr. (1849.) Ann. Phami. 69, 323. 

Yellow TYiehhrkydroehinone, 

When terchlorkinone is boiled with a qnantity of aaueons salphurong 
acid, less than sufficient to convert it into terchlorhjarokinone, a red* 
brown liaaid is formed, on which there float brown viscid oil-drop.<3y 
probably oelonging to this compound; in a larger quantity of sulphurooa 
acid, they dissolve without colour, as chlorhydrokinone. 



CMorine-nueleua C^*C1*0«. 

Ghloranil. 

Ebdmann. (1849.) J. pr. Client, 23, 273 and 279. 
A. W. HoPMANN. Ann, Pharm, 52, 55, 

Formation. 1. From carbolic acid, kinone (Hofmann), aniline 

iFritzche), chloraniline, binitrocarbolic acid or ternitrocarbolic acid 
Hofmann), when either of these compounds is heated with hydrochloric 
acid and chlorate of potash. — 2. Similarly from salicylous acid, salicylic 
acid (also, according to Cahonrs), nitrosahcylic acid, or anthranilic acid^ 
with evolution of carbonic acid. (Not from benzoic acid or its allied 
compounds.) (Hofmann.) — 3. From kinic acid when heated with common 
salt, peroxide of manganese, and sulphuric acid, — together with car- 
bonic acid, the three chlorkinones, &c. (Stadeler.) — 4. From isatin^ 
when boiled with hydrochloric acid and chlorate of potash (Laurent); 
from alcoholic chlorisatin or bicblorisntin by the action of chlorine gas 
(Erdmann); or more quickly by hydrochloric acid and chlorate of potash, 
— whereas indigo treated in the same manner, gives only traces of this 
compound. (Hofmann.) — 5. From pyrocatechin, C"H*0*, by the action 
of hydrochloric acid and chlorate of potash (R. Wagner, J, pr, Chem, 
67,441): 

C«H«0^ + lOCl = C»2C1<0< + 6HC1. 

Preparation, Strong hydrochloric acid is poured upon carbolic acid 
in a basin; chlorate of potash added in small crystals; and the mixture 
heated as soon as the first violent action, which may amount to explosion, 
is over, the heating being continued for some time, till in fact the 



CHLORANIL. 107 

• 
carbolic acid, which at first becomes thick and red-brown, is converted 
into a light yellow crystalline mass, which, after washing with water, 
may be crystallised from boiling alcohol. The transformation takes 
place more quickly when the carbolic acid is dissolved in boiling water 
or in alcohol; but if alcohol be used, it is necessary, on account of the 
readiness with which explosion takes place, to use more dilute hydro- 
chloric acid and to add the chlorate of potash gradually. (Hofmann.)— • 
2. By boiling kinone (Hofmann^, or the wash-water obtained in the 
preparation of kinone by Wohler*s process (p. 159), which contains 
kinone in the state of very dilute solution (Stadeler), with hydro- 
chloric acid and chlorate of potash. — 3. Similarly, binitrocarbolio or 
ternitrocarbolic acid dissolved in water or alcohol. (Hofmann.)— 4. Also 
salicylous acid, salicylic acid, nitrosalicylio acid, or salicin. The last 
muse be dissolved, together with chlorate of potash, in boiling water, and 
small quantities of hydrochloric acid then added, whereupon the solu- 
tion immediately acquires a deep orange-yellow colour, and becomes 
covered with a crust of small crystals of chloranil, amounting to 30*27 p.c. 
of the salicin. If the salicin be first heated with hydrochloric acid alone, 
saliretin is formed, which, when afterwards heated with chlorate of 
i>ota8h, does not yield any chloranil. (Hofmann.) — 5. When a salt of 
kinic acid is distilled with common salt, peroxide of manganese, and 
aqueous sulphuric acid (p. 1 86), a portion of the chloranil thereby pro- 
duced sublimes in the upper part of the flask and in the distillation-tube, 
a considerable portion, however, remaining in the residue. (Stadeler.) — 
6. Chlorine gas is passed through 80 per cent, alcohol in which chlor- 
isatin or bichlorisatin is dissolved or suspended, till the thick oily liquid 
which falls down no longer increases, and nothing more is formed than 
products of decomposition of the alcohol; the oily liquid, after removal 
of the sal-ammoniac by water, is exhausted with cold alcohol, which dis- 
solves chlorinated chlorindoptene and a resinous substance, together with 
heavy hydrochloric ether and other products of decomposition of the 
alcohol, and leaves the greater part of the chloranil in the crystalline 
form. The alcoholic solution evaporated to a syrup aud cooled yields an 
additional quantity of chloranil crystals to be purified by exhaustion 
with cold alcohol; and the alcoholic liquid thereby obtained, yields still an 
additional quantity by repetition of the process. The whole of the 
chloranil crystals are washed with water, and finally purified by repeated 
crystallisation from hot alcohol, or by sublidiation — a small quantity of 
charcoal then remaining — and washing the sublimate with cold alcohol, 
(Erdmann.) — 7. Pulverised isatin is added to boiling hydrochloric acid, 
then chlorate of potash; and the resulting soft mass mixed with crystals, 
is washed with water, thrown upon a filter together with a little ether, 
washed with cold alcohol, and purified by crystallisation from hot alcohol, 
or by sublimation. (Laurent; Rev, scient 19, 141; abstr. J.pr, Ckem. 
36, 277.) 

Properties, Pale yellow (golden-yellow according to Hofmann), 
nacreous, often iridescent lamina?. (Erdmann.) Volatilises completely at 
a gentle heat without fusion, and without leaving any residue of char- 
coal (slowly at 150°, quickly between 210° and 220°: Hofmann)^ in 
yellow vapours, which condense on cold bodies in delicate laminse, and 
on hot bodies in the form of a liquid, solidifying to a sulphur-yellow 
crystalline mass on cooling. Larger quantities of chloranil, when rapidly 
heated, melt partially into a dark brown boiling liauid^ and leave ^ smaU 



198 BBNZENE : CHLORINS^NUCLEUS C^IK)>. 

qnantity of charcoal. — The alcoholic solution has uo action o^ Y^eteble 
colours. (Brdmana.) 

Erdmann. Hoftiiaiiii. IiamrQiit. 

J^V^oin aleokoL Sublimed. 

12 C... 72'0 .... 2M1 .... 30a3 .... 89-83 ... 3014 .... 2^-50 

4 CI 141-6 ,... 57'66 .... 67*60 .... 67*74 .... 66*20 

4 32-0 .... 1303 .... 11-77 ,... 1244 .... 1332 

H 0-34 



^mm 



C^Cl^O* .... 245-6 .... 10000 .... 10000 .... lOO'OO .... 10000 



DeeompiMtiioru. 1 . Chloranil dissolves y^rj readily apd with dark 
purple colour (after previously assuming a greenish black colour : H<^' 
mann), in warm dilute paUuh, in the form of chloranilate of potash^ which 
soon crystallises, and chloride of potassium. 

C»C1^0< + 4K0 - C»Cl«K«08 + 2KCI. (Erdmann.) 

When strong potash is used^ part of the product is further decomposed, 
so that the brown-red solution yields but a small quantity of chloranilate 
of potash, and a dark mother-liquor which is not precipitated by hydro- 
chloric acid. (Erdmann.) -«** 2. It dissolves slowly and with deep blood*red 
colour in aqueous ammonia, forming oliloranilammone (cbloranilaroate of 
aoinioniay acoordiug to Laurent) wbtch crysiaUi^es ont^ and aal-ammoBiac: 

C"CHO* + 4NIl» + 2H0 » C»«N«a«Il«0« + 2N«*a. 

3. ChloranQ gently het^ted with alcohol to which ammonia is adde^* 
yields brown-red cblon^nilamide which remains undissolved* together 
with a solution of chloranilamate of ammonia and another substance : 

C»»CI*0* + 4NH» - C»N»a»H<0* + 2NH<C1. 

If absolute alcohol and ammoniacal gas were used, the chief product 
would probably be chloranilamide. (Laurent.) — i. The yellow solution 
of chloranil in aqueous monosulphide of potassium^ quickly mixed with 
hydrochloric acid, without contact of air, yields a precipitate which ha^ 
a sulphur-yellow colour when dry. This precipitate, when heated, yields 
a few colourless needles and {aminse, then melts and decomposes, giving 
off sulphurous acid. It dissolves in alcohol and ether, and with rej- 
brown colour in potash. When purified from any free sulphur that may 
be mechanically mixed with it, by treating it with sulphide of carboni 
whereby it is partially dissolved, it contains 8*1 p. c. sulphur and 51*8 
chlorine. On exposure to the air, the yellow solution of chloranil in 
raonosnlphide of potassium, quickly turns red, then brown, then black> 
and deposits a black granular powder, which contains sulphur and 
potash, and does not dissolve in water or alcohol. The yellow solution 
of chloranil in ordinary liver of sulphur, becomes yellowish red on 
exposure to the air, then assumes a continually deeper purple, and at 
last a black colour, first depositing sulphur and afterwards a black 
powder. (Erdmann.) — 5. Chloranil boiled with aqueous sulphurous 
acid, takes np 2H and is converted into chlorbydranil. (Stfideler.) 

Chloranil is not decomposed by sulphuric, hydrochloric, or even by, 
boiling nitric t^cid (or by boiling aqua-regia« or by chloride of lime ; 
iStenhgnm); neither is any decomposing^ antion exerted upon U 1/ M 



CMLOBHTDRANIL. 199 

alooholio solution of iodide or bromide of potassiam when boiled, or bj 
cyanide of meroarj when eublimed with it. (Erdmann.) 

Combinatiotu. Chloranil is insolable in water. (Erdmann.) 
It is nearly insolable in cold alcohol, bat dissolves sparingly in 
boiling alcohol, forming a yellow solution which changes to light violet 
on exposure to the air, and deposits nearly all the chloranil on cooling. 
(Hofmann.) 

In ether, it dissolres somewhat more freely. (Hofmann.) 



Ghlorhydranil. 

C«C1*H*0* = C"C1*0»,H*0\ 
Stadelbr. (1849.) Ann. Pharm, 69, 327. 

FormcUum and Preparation. Crystals of chloranil' are boiled with 
aqneous salphurous acid till they exhibit no further change of colour; 
the then brownish white crystals collected on a filter, washed with cold 
water, and dissolved, after drying, in a mixture of ether and weak 
alcohol; the solution left to evaporate till it crystallises; the mass of 
brownish white lamin» dissolved in strong boiling acetic acid; and the 
solution filtered from a brownish tenacious mass, and cooled to the crystal- 
lising point. 

Properties, Delicate white nacreous lamins^. They do not alter at 
50"" but become sliKhtly brown at 160^ strongly between 215^ and 220""; 
sublime rather quickly at th^t temperature, but do not melt till more 
strongly heated, and then solidify in - a crystalline mass on cooling. 
Inodoroiu and tasteless. In solution it reddens litmus. 

Stadeler. 

12 C 720 .... 2908 29'46 

4 CI 141-6 .... 5719 

2 H 20 .... 0-81 0-90 

4 32-0 .... 12-92 



CWC1«H«0* 247-6 .... 100-00 

Decompositions, 1. By hjrpochlorite of soda, most readily when a 
small quantity of that salt is added by drops to its solution in a small 
quantity of alcohol, it is converted into needles of a deep green colour, 
which, when heated in a test -tube, give off chloranil and leave charcoal, 
and are soluble in water and in alcohol. — 2. When heated with water 
containing a small quantity of nitric acid or sesquiohloride of iron, it 
turns yellow ; also when its hot solution in weak alcohol is mixed with a 
hot solution of nitrate of silver, the silver being then deponited in the 
specular or pulverulent form; and the hot filtrate, on cooling, yields 
delicate rhombic laminsa, perhaps of C^'Cl*HO* [or of chloranil ?]. — 
S. Its hot-saturated solution in potash-ley deposits on cooling a consi- 
derable number of prisms of a potash salt, which, as well as its solution, 
quickly turns red on exposure to ibe air. — 4. Its yellow solution iu 



200 BENZENE : SULPHOCHLORINE-NUCLEUS C»3C1H\S02). 

warm aqueous ammonia tornfi violet when mixed with bjdrocbloric acid, 
and forms with chloride of calcium, after a while, a crystalline preci- 
pitate which chances on exposure to the air. The same solution exposed 
to the air in a basm turns green from above downwards, then gradually 
deposits a green crystalline powder, and becomes red. — Chlorhydranil is 
neither decomposed nor dissolved by warm oil of vitriol 

ComUnations, — Chlorhydranil is insoluble in water. 

It dissolves with yellow colour in aqueous ammonia, especially when 
heated, and readily and without colour in cold dilute pota^, wherein it 
is precipitated in the crystalline form by hydrochloric acid. 

Its alcoholic solution forms a white precipitate with neulrol acetate 
of lead. 

It dissolves readily in qfcohol and in ether, (Stadeler.) 



IT Stdphochlorine^udeus C"C1H*(S0»)» 

Chlorosulphobenzene, 

C"C1H*(S0»). 
H. GerickBi Ann, Pharm. 100, 213. 

Formed by the action of chlorine on sulphobenzene. Chlorine gas 
acts upon dry sulphobenzene, even in the cold^ and especially in sunshine, 
forming the hydrochlorate of chloroeulphobenzene, contaminated how- 
ever with undecomposed sulphobenzene. But by passing chlorine gas 
over melted sulphobenzene, the hydrochlorate of chlorosulphobenzene is 
obtained in a purer state and in yellow oily drops, which may be further 
purified by repeated solution in alcohol and precipitation by water This 
hydrochlorate, when suddenly heated, is resolved into hydrochloric acid 
and chlorosulphobenzene, which separates in the neck of the retort as a 
yellow crystalline mass. It is also separated by digesting the hydro- 
chlorate with alcoholic potash, whereby a precipitate of chloride of 
potassium is formed, and the filtrate as it cools deposits crystals of chloro- 
sulphobenzene, which may be purified by washing with water and 
recrystallisation from alcohol and ether. 

Colourless crystalline mass, which, under the microscope, appears to be 
formed of long acuminated crystals. Melts at about 152°, and solidifies 
again in the crystalline form, but sublimes at temperatures much below 
its melting point. By repeated melting and cooling, the melting point 
sinks to 64°. It is decomposed by boiling with alcoholic potash, unaltered 
chlorosulphobenzene passing over at first with the alcohol-vapours, but 
afterwards sulphobenzene passes over in oily drops which solidify in the 
crystalline state, and charcoal remains in the retort. Chlorosulpho- 
benzene is not reduced to sulphobenzene by the action of zinc and sulphuric 
acid. It is insoluble in water and in dilute acids, alkalis, and alkaline 
carbonated. 

Hydrochlorate of Chlorosulphobenzene, — Preparation (nd, Bup,). Yellow 
oily drops, heavier than water^ having an odour like that of sulphite of 



MITROD&NZBNE. 201 

chlorobenzene (p. 174) and a disagreeable taste. Has no action upon 
litmus. Distils without decomposition at 150^. 

Gericke. 

12 C 72-0 .... 400 40-2 

5 H 50 .... 2-8 30 

2 CI 70'8 .... 39-4 37*2 

2 S 160 .... 8-9 

2 O 160 .... 8-9 

C«CIH<(S02),HCI.... 179-8 ... 1000 
Gericke doubles the formula of chlororalpbobenzene, making it C3«Cl'H^(S02)'y and 
tiie hydrochloratc C«a«H8(SO»)',2HCl. 



The hjdrochlorate burns on platinum-foil, with a smoky flame and 
disagreeable odour. It is not decomposed or dissolved bj dilute alkalis 
or bj dilute sulphuric or hydrochloric acid. Nitric acid acts upon it with 
evolution of red vapours and probably forms a nitro-compound. Heated 
with iodide of potassium, it forms a blood-red liquid. 

It is insoluble in water, but dissolves in alcoJuil and ether. When 
exposed to the air, it absorbs water and evaporates quickly. (Gericke.) IT 



NUro-nudetu C«XH». 

Nitrobenzene. 

C"NHW = C»XH». 

I 

MiTSCHEBLiCH. (1834.) Fogg, 31, 625. 

Nitrobenzolf Nitrobemin, Nitrobenzid, Nitrobenzituise, Nitrofune, 

Fofmation. 1. By heating benzene with fuming nitric acid. (Mits* 
cherlich.) — 2. By the dry distillation of nitrpbenzoate of silver. (Mulder, 
J. pr. Chem. 19, 375.) 

Preparation, Benzene is added by small portions to warm fuming 
nitric acid, and the nitrobenzene which separates on cooling washed with 
water. (Mitscherlich.) Hilkenkamp {Ann, JPkartn. 95, 86) adds the 
benzene to cold faming nitric acid. 

Properties, Needles at 3°; above S°, a yellowish liquid of sp. gr. 
1-209 at 15°; boils at 213° Vapour-density 44. Smells like bitter 
almond oil and cinnamon oil; tastes very sweet (Mitscherlich.) 

Mitscberlich. Mulder. 

12 C 72 .... 58-54 .... 5853 .... 58-35 

N 14 .... 11-38 .... 11-70 

5 H 5 .... 4-06 .... 4-08 .... 4-07 

I 4 O 32 .... 2602 .... 25*09 

C«N»*Q» ,, 123 .... WOO .... 10000 



202 BBNZBNE: NITRO-NUCLBUS CUXH*. 

Vol. Density. 

C-vaponr 12 4*9920 

N-gaa 1 0-9706 

H-gM 5 0-3465 

O-gas 2 2-2186 

Vftpour of NUrobemene 2 8*5277 

1 4-2638 

Deoompowtiora, Nitrobenzene passed in the state of vapour through 
a hot tube, together with chlorine gas, is decomposed, with formation of 
hydrochloric acid. (Mitscherlich.) — 2. Bj boiling with fuming nitric 
acid, it is converted into bin itroben zone. (Deville.) — 3. When heated 
with oil of vitriol it becomes strongly coloured and eliminates sulphurous 
acid gas. — It is not decomposed at ordinary temperatures by chlorine or 
bromine, or when heated with moderately strong nitric or dilute sulphuric 
acid. — 4. Nitrobensene is but little affected by aqueous potash or 
ammonia at a boiling heat, or by lime when distilled over it; but with 
boiling alcoholic potash it forms a red liquid, which when distilled yields 
azobenzene C^N'H^^ in the form of a red liquid crystallising as it cools^ 
whilst a peculiar potash-salt remains in the retort (Mitscherlich.) In 
this process, aniline also distils over, and at a later stage a largft 
quantity of oxalic acid is found in the residue. (Hofuiann k Muspratt, 
Ann Pkarm. 54, 27.) — The solution of 1 vol. nitrobenzene in 8 vol. 
strong alcohol boils, bn addition of a quantity of hydrate of potash equal 
to that of the nitrobenzene, assuming at the same time a dark brown-red 
colour, and, after the boiling has been up for some minntes by external 
heating, deposits yellowish brown needles of azoxybenzene, C'*N'H*^0', 
and, when the alcohol is distilled off, separates into two layers, the lower 
of which contains potash, carbonate of potash, a brown potash-salt 
easily soluble in water, nearly insoluble in alcohol (whereas the brown 
acid contained in it dissolves in alcohol but not in water), and an indifferent 
dark brown powder, sparingly soluble in water and alcohol, whilst the 
npper layer is a dark brown oil which, on cooling, gradually solidifies into 
needle-shaped azoxybenzene (amounting to half the nitrobenzene^. 
This azoxybenzene when distilled, yields azobenzene, with a nearly equal 
quantity of aniline. (Ziuin, J. pr. Chem, 36, 98.) Laarent & Gerbardt 
{Compi, Chim. 1849, 417 ; also Ann, Pharm, 75, 70) endeavoured to find a fonnala 
for this decomposition by alcoholic potash. — 5. When sulphuretted hydrogen is 
passed through nitrobenzene dissolved in alcohol and mixed with 
ammonia, crystals of sulphur are deposited, the liquid loses the odour of 
sulphuretted hydrogen, and solidifies at 0° after some time into a mass 
of delicate yellow needles, which have a biting taste and dissolve readily 
in water and alcohol; this crystalline mass, when freed by distillation 
fi'om part of the alcohol, continually deposits sulphur and ultimately 
loaves aniline. (Zinin.) 

C»NHH>« + 6HS - a*SW + 4H0 + 6S. 

6. It is quickly converted into aniline when placed in contact with zino 
and a mixtnre of alcohol and hydrochloric acid in equal volumes, 
(Hofmann, Ann, Pharm. 5.0, 201.) 

CKNH*CM + 6H - C^VBJ + 4H0. 

% 7. Aniline is also produced by the action of ferrous acetate upon 
nitrobenzene: 

C«NI1*0* + l2FeO + 2H0 - 6Fe'Q» + Q«NH7. 



NITROCABBOLIC ACID. 203 

Ferrous tnlphaie, oxalate and hydrocblorate do not act npon nitrobenzene. When 
1 pt. of nitrobenzene, i|-pt. iron filings, and 1 pt. ooncentrated acetic acid 
are introduced into a retort, a brisk action commences without external 
beating, and the distillate, which must be collected in a well-cooled 
receiver, consists of aniline, acetate of aniline, and undecomposed 
nitrobenzene : 

Ci^NH'O* + 4Fe + 2H0 - 2Fe20» + C"NH7. 

On pouring the contents of the receiver into the retort after cooling, 
distilling to dryness, and treating the distillate with potash-ley, aqueous 
aniline separates out. (A. B6champ, y, Ann, Chitn, Phys. 42, 186.) — 
8. Nitrobenzene heated to the boiling point for some hours with dry 
.sulphite of ammonia and absolute alcohol, with addition of carbonate of 
ammonia to keep the liquid alkaliue (otherwise the principal product is 
decomposed by the sulphurous acid evolved) yields, after the liquid has 
been left to cool, filtered from the sulphate of ammonia which sepa- 
rates out, and evaporated to an oily consistence, also with addition of 
carbonate of ammonia, — a large quantity of delicate white laniinie 
which quickly decompose, and a smaller quantity of fine hard needles 
consisting of the ammonia-salt of dithiobenaolic or phenj/ldisulpho-diamic 
acid [C"N«H»S*0" ^ C»Ad^H*S*0"], the formation of which appears to 
be due to the action of the sulphite of ammonia on binitrooenzene 
C"(NO*)*H*, contained in the nitrooenzene. 

C"(NO*yH* + 12(NH*0,S0S) - CMAd»H«(NH*)«,S^OW + 8(NH<0,80») + 2NH». 

The laminie probably consists of the ammonia-salt of thiobemdic, phenyl^ 
disulphamic, or disulpkaniiic add [C^'AdH^S'0*J, formed by the action of 
sulphite of ammonia on the nitrobenjEeoe itself. 

[CM(NO<)H» + 6(NH*0,S0») = C»AdH\NH*).S»0« + 4(NH^O,S6») + NH». ] 

(L. Hilkenkamp, Ann, Pharm. 95, 86; Ckem, Gaz, 1855, 461.) IT. 

Combinations, Nitrobenzene is insoluble in water. 
It dissolves readily in strong sulphuric or nitric acid, especially when 
heated. 

It mixes in all proportions with alcohol and ether, (Mitscherlich.) 



Nitrocarbolic Acid. 

C'*NH*0« = C»XH*,0» 

Mononiirophenol, tinfaeh-NUrophenolt NitrocarboMure, 

Formation. 1. By treating carbolic acid with nitric acid. — 2. By 
treating aniline with nitric acid and arsenions acid. ^- 8. By passing 
nitric oxide through a solution of aniline in rather strong nitric a«id, a 
brown rosinons mixture is obtained, consisting of crystalline nitrocarbolic 
acid with a brown amorphous substance and a trace of carbolic acid. — 
Nitrocarbolic acid is a beautiful crystalline body. (A. W. Hofmann, 
Ann, Pharm, 15, 358.) 



204 BENZENE: NITRO-NUCLEUS C^X^H^ 



NUrcchlonne-nucIeiis C"XCIH*. 

Nitrochloroniceic Acid. 

C»NC1H*0« = C"XC1H^0^ 

St. EvBE. (1849.) N.Ann, Chim. Phy$, 25, 492j vXso Ann, Pharm. 
70, 261. 

Acide chloronicSique nitr4, Nitrochloronicensdure, 

Crystallises on cooling from a solution of cliloroniceic acid in fuming 
nitric acid and is purified by crystallisation from alcohol. 
Broad micaceous laminad having a fatty lustre. 



12 C 

N 

CI 

4H 

80 







St Erre. 


72-0 


.... 38-02 .. 


37-83 


14-0 


.... 7-39 .. 


7-77 


35-4 


.... 18-69 .. 


18-35 


4-0 


.... 2-11 .. 


2-25 


64*0 


.... 33-79 .. 


33-80 



C^NCIHW 189-4 .... 100-00 10000 



Nitrochloroniceic Ether. 

C"NC1H»0« = C*H«0,C"XC1H»0». 



Broad colourless laminaa. (St. Evre.) 



16 C 


96-0 


.... 44-16 
6-44 

.... 16-28 
3-68 

.... 29-44 


St. Evre. 
43-75 


N 

CI 

8 H 


140 

36-4 

680 


6-69 

15-78 

3-74 


8 


64-0 


30-04 








C>•^X1H«08 


217-4 


.... 100-00 


10000 



Niiro-nucleus C»X»H*. 

Binitrobenzene. 

C»N'H*0« = C"X*H*. 

Detille. (1841.) iV^. Ann. Chim, Fhyt, 3, 187; also J, pr. CJiem. 

25, 353. 
MuspRATT & A, W. HoFMAKN. Phil. Mag, J. 29, 318; also Ann, Pharnu 

57, 214. 

Biniiroberuol, Dinitroben^f Bimtrobtnzidef Nitrobenjfm^^^ 



BINITROCARBOLIC ACID. 205 

Preparation, A solution of 1 pt. niirobenzeue in G pis. fuming nitric 
acid 18 boiled down to 1*4 pt., the acid removed from the residue by 
washing with water and then crystallised from alcohol. (Deville.)-— 
2. Benzene or nitrobenzene is dropt^ as long as it dissolves^ into a mix- 
ture of equal parts of fuming nitric acid and oil of vitriol; the solution 
boiled for some minutes; and the crystalline magma which forms on 
cooling, washed with water, and left to crystallise from alcohol. 
(Hofmann & Muspratt) 

Properties. Long shining needles and laminaa which melt below 100% 
and solidify in a radiated mass on cooling. (Deyille.) 



12 C 

2N 


72 

28 


.... 42-86 
.... 16-66 ... 

.... & Ori 

.... 3810 ... 


Deyille. 

42-70 . 

17-10 

2-56 . 

37-64 


Hofmann 
& Maspratt. 

43-26 


4 H 


4 


3'42 


8 O 


64 










C"N2H^08 


.... 168 


.... 100-00 ... 


10000 





Binitrobenzene boiled with sulphite of ammonia and absolute alcohol 
18 converted into dithiobenzolate of ammonia. (Hilkenkamp, see p. 203.) 
It dissolves very readily in hot alcohol. (Deville.) 



Binitrocarbolic Acid. 

C»N»H*0" = C'«X»H*,0«. 

liAunfiNT. (1841.) N. Ann. Chim. Phys, 3, 213; also Ann. Pharm. 49, 
213; also </. pr. Chem, 25, 416. 

■ 

BinUrocarbolsduref Nitrophdnenaure, Acide fUtrophcnenque, 

Thrmation, 1. By the more moderate action of nitric acid upon 
carbolic acid. (Laurent): 

C»H«0« + 2N0» - CJ*N»H<0» + 2H0. 

2. By boiling binitranisol (C"X»H»0»<^) with alcoholic potash. (Cahoura, 
N. Ann, Chim, Phys, 25, 22.) 

Preparation, 12 pts. of commercial nitric acid are added by sepa* 
rate portions in a large porcelain basin to 1 pt of that portion of coal-tar 
oil which boils between 160^ and 190% a fresh portion being added as 
soon as the violent intumescence caused b}* the preceding has subsided, in 
which case the mixture becomes hot enough to render external heating 
unnecessary. The resulting thick red-brown mass is freed by water from 
the greater part of the nitric acid; the residue boiled with very dilute 
ammonia; the solution while hot rapidly filtered from a brown resinous 
mass which serves for the preparation of picric acid; the brown crystal- 
line substance which separates within 24 hours from the dark brown 
filtrate, collected (an additional quantity of the brown r#8inou8 mass 



206 BENZENE J NITRO-NUCLEUS C*«X«tt*. 

serving for tbe preparation of picric acid, maj be precipitated from tlie 
mother-liquor hj acida); the crystalline substance dissolved in boiling 
*water; the delicate neeales of binitrocarbolate of ammonia which form on 
cooling, purified by four recrystallisations (the matter precipitated from 
the mother-liqoors by nitric acid serves for the preparation of picric 
acid^, washed with cold water, and dissolved in a very large quantity of 
l>oilmg water; the solution filtered as quickly as possible from any of the 
brown mass that may be precipi.tated; the mother-liquor decanted from 
the acid which crystallises on cooling, boiled with fresh ammonia, again 
mixed with nitric acid Ac, and finally, the acid, which is thus obtained 
crystallised in fork^ike tufts, is dissolved in boiling alcohol to purify it 
from a small quantity of oil : it then crystallises free from oil on cooling. 
(Laurent) 

Properiiea, Pale brown yellow prisms belonging to the riflht prismatic 
system. Fig. 56, tr :t=U5^; % : <=127**; u : i*=50''andl30^(J?«;. acient. 
9, 24). Melts at 114°, and solidifies in a radiated mass on cooling. May 
be distilled in small quantities without decomposition. Inodorous; taste- 
less at first, afterwards very bitter. Colours the cuticle, horn, and other 
animal tissues, deep yellow. (Laurent.) 



12 C 


H 


.... 15-22 .. 
2'17 

• ••• mm A § •• 


Laurent. 

.4.... Ov-Qv ..• 

15;6 ... 

2-28 ... 

42-61 ... 


Cahoart, 
39-18 


2 N 

4 H 


28 

4 


15-21 

2-17 


10 O 


80 


43-44 








C>*X«HH)» 


.... 184 


.... 100-00 .. 


10000 ... 


10000 



Decompontions. 1. The acid detonates when suddenly heated in a 
tube, or slightly, when heated in the air, with red fiame and black 
smoke, leaving a residue of charcoal. — 2. When heated with bromine, it 
IS converted into binitrobromocarbolic acid. (Htv. acient. 6, 95.) Chlorine 
appears not to act upon it — 3. By boiling nitric acid it is quickly 
converted into pi( ric acid. (Laurent.) — 4. When heated with chlorate 
of potash and hydrochloric acid, it is very easily converted into chloranil. 
(Hofmau, Ann. Pharm. 52, 62.) — 5. It dissolves in warm fuming oil of 
vitriol, and then decomposes, with lapid erolntion of gas, tnrningbrown 
and thickening at the same time. — 6. It dissolves gradually in dilute 
sulphuric acid, in presence of sine, forming a rose-coloured liquid, which 
is turned green by excess of ammonia, without precipitation. — 7. When 
digested with aqueous oil of vitriol and baryta, out of contact of air, it 
forms a blood-red liquid. (Laurent) — 8. When gently heated with 
aoueous hydrosulphate of ammonia, it forms a nearly black liquid, 
which, on cooling, deposits black-brown needles of nitrodifunamio acid, 
C~Ad»X»H»,0*+4Aq; thus: 

2C»JS'H*0** + 12HS = C«*N*H"0" + 4H0 + 12S. 

(Laurent and Gerhardt, Ann, Pkarm, 75, 68.) 

Combinati/ona. Tbe acid is nearly insoluble in cold water^ and dis- 
solves but sparingly in boiling water. 

It dissolves abundantly in warm otZ of vitriol, whence it is precipi- 
tated by water. 

It dissolves slightly in boiling hjfdroehloric aeidj and sepanUes in 
{em-like tofts on eooling. 



MUltllOCARBOLIC ACID. 207 

The Biniiroearbolates or Nitrophenesatei are obtained, sometimes by 
saturating the acid with the pure base or its carbonate, sometimes by 
double decomposition. They are yellow or aurora-red and crystallisable. 
They all dissolve in water, and in this form impart a strong yellow 
colour to animal tissues. Heated somewhat above the melting point of 
lead, they detonate very slightly, with emission of light. Sulphuric, 
hydrochloric and nitric acid separate the acid from them. 

Binitrocarholate of Ammonia. — Crystallises from boiling water in 
long thin yellow needles having a silky lustre. By sublimation, yellow 
shining laminae are obtained. Fig. 68, without p and f ; « : < = 144° 30'. 
{Rev. scieni. 9, 26.) Very sparingly soluble in water, still less in alcohol. 
(Laurent.) 

Binitrocarholate of Potash, — Yellow, shining, six-sided needles, with 
angles of 115°. They redden whenever they are heated, without alten^ 
tion of weight; decompose and become opaque below 100°; give off 
d'90 p. c. water in vacuo at 100°; melt at a stronger heat, and then 
detonate. They dissolve sparingly in cold water^ very sparingly in cold 
alcohol, more easily in hot alcohol. (Laurent.) 

Lauront. 

C"N«H»0» 1750 .... 75-6d 

KO 47-2 .... 20-42 20-14 

HO 90 .... 3-89 3-90 



•i*^.ta_i^b>^.^.bM^.^^— ^k^i^ 



C"X*H»KO> + Aq 231-2 .... 10000 

BinUroearbolaJte of Soda. — Yellow, silky needles, which dissolve 
pretty easily in water. (Laurent.) 

Binitrocarholate of Baryta. — Aurora-red (like bichromate of potash), 
thick, six-sided oblique prisms and needles, with two angles of the lateral 
edges of 89°, and four of 13/^° 3tf « In vacuo, at ordinary temperatures, 
they give off Q'5 p. c. (2 At.) and at 100° altogether, 1542 p. c. (5 At.) 
water. 

CrytaU. Laurent 

Ci2N5HK>» 1750 .... 59-00 

BaO 76-6 .... 25-83 25-62 

5 HO 450 .... 15'17 15-42 

C«X«H»BaO» + 5Aq.... 296-6 .... 10000 

The ammonia-salt, mixed with chloride of ttroniium, the solutions 
being hot and concentrated, soon forms silky needles; with chloride of 
calcium, granules consisting of needles; with alum, needles. It does 
not precipitate salts of magnesium, manganese, cadmium, eobaU, nickel, 
or capper, or mercuric salts.' 

Binitrocarholate of Lead. — a. Bibasic. — The yellow precipitate 
which the ammonia-salt produces in a boiling dilute solution of neutral 
acetate of lead. It detonates with peculiar violence when heated, and 
gives off 8*4 p. c water in vacuo at ordinary temperatures, 9*4 p. c. In 
ail at 100°. 

6. Sesquibasic, — The boiling, moderately concentrated mixture of alco- 
holic binitrocarboHo acid and alcoholic acetate of lead, yields on cooling, 
microscopic needles grouped in yellow balls, which do not give off any 
water at 150^ (Laurent.) 



BENZENE: NITROBROMINE-NOCLBUS C'X'BrH'. 
Salt a. LanrenL 



cwwo* 

2 PbO _ 


175 .. 

224 .. 


.. 40-23 
.. 51-49 .... 
8-28 ,.„ 


.... 50-6 









PbO.C'^'H'PbO' + 4Aq 435 



2 C'WH'O' 350 ... 51-02 

3 PbO, ., 330 .... 48-98 



PbO,2C'>X'H»PbO» 6BG .... 100-00 

BinitrocarbolaU of Cobalt. — ■Brown-yellow, right recUngitlar prisma, 
vith dihedral eummits. Its brown aqueoas solution forme with ammonia 
a yellow precipitate vhich melts and detonates when heated. (Laarent.) 

Bittiirocanolate of Copper. — Yellow silky needles, whose yellow 
Bolntjon forms with ammonia, yellow needles sparingly solnole in 
ammonia or in water. (Lanrent.) 

Binitroearbolate of Silver. — The ammonia-salt forms with solntion of 
nitrate of silver, a reddish yellow precipitate, or in case of greater dilu' 
tion, after a while, needles which dissolve in a large quantity of water 
or alcohol. (Laurent.) 

Binitrocarbolio acid dissolves rery readily in altohol and in et^r. 
(Laareut.) 



JTrtrofowminf-ntwfeu* C^X'BrH'. 

Biuitrobromocarbolic Acid. 
C^N'BrHK)'* = C"X'BrH',0*. 

Lavbbnt. Bev. teteTit. 6, 65. 

BinitroinmoearioUdtirt, Aetdt nitmhrOBiepMiitijHe. 

nitrocarbolio acid is dissolved in heated bromine; the 
e on cooling, washed with asmall qnanljty of aloohol, 
ng ether; and the solution left to ctystallise in a 
with paper. 

hur-yellow, traDSparent. Crystallises from etiier in 
bic prisms. Fuj. 81, the comers between «, w' and «, 
faces, which form willi u or u' an angle of abont 
30'; i:v or u' ~ SS" 30'. — From toiling water or 
n needles. Melts at about 110°, and soiidiGea on 
r fibrous mass. When strongly heated, it distils 
and leaves a small Quantity of charcoal. Permanent 
coloars the skin yellow, like picric acid. 



BINITROBROMOCARBOLIC ACID. 209 

OeyHalt. Laurent. 

12 C 72 .... 27-37 27*49 

2N 28 .... 10-65 11-20 

Br 80 .... 30-42 29-50 

3 H 3 .... 1-14 1-20 

10 O 80 .... 30-42 30-61 

CP*N«BrHH>w 263 .... 10000 100-00 



Decompositions^ 1. The acid is not decomposed by chlorine in the 
cold and but e^ightly when heated. — 2. By boiling nitric acid it is con- 
verted into picric acid. — 3. Its solution in warm oil of vitriol decom- 
poses when heated. — 4. Its aqueous solution forms with ferrous sulphate 
and lime, a blood-red liquid, with precipitation of ferric oxide. 

Combinations. The acid dissolves very sparingly in boiling tocUer. 
and separates almost completely on cooling. 

It dissolves in warm oil of vUriol, whence it crystallises in fern-like 
groups. 

The Binitrohromocarbolates or NitrohromophenisaUs are yellow, orange- 
coloured or red; crystallise well; resemble the picrates; detonate for the 
most part, like those salts, when heated, but less strongly, and in a closed 
space, with emission of light; and dissolve for the most part in water, 
from which solution, sulphuric, hydrochloric, or nitric acid separates the 
binitrobromocarbolic acid. 

Binitrobromocarbolate of Ammonia. — Yellow eight-sided needles 
derived from a rhombic prism. In vacuo at 100° they give off 8*57 p. c. 
water, and 1*86 p. c. more at a heat nearly sufficient to volatilise them, 
and then sublime, for the most part undecomposed, in yellow, shining right 
rhombic prisms, with lateral edges of 45^ and 135^ 

The potashrScUi forms yellow, silky needles, sparingly soluble in water 
and alcohol. 

Baryta-salt, — The dark yellow needles, which dissolve very readily 
in water, give off in vacuo at ordinary temperatures, 7 '5 p. c. (3 At.) 
water, assuming a scarlet colour, and at 100°, 9*42 p.o. (4 At.) in all. 

CryitaU, Laurent. 

C»N»H«09 174-0 .... 47-47 

Br 80-0 .... 21-82 21-8 

BaO 76-6 .... 20-89 20*5 

4 HO 360 .... 9-82 942 

Ci3N'BrH'BaOio+4Aq 366-6 ....10000 

Lime-salt. — Long yellow lamina, which are oblique rectangular 
prisms. They turn about on recently dried paper or in vacuo, giving off 
water and assuming a scarlet colour. 

The ammouia-salt doee not form any precipitate with chloride of strontium, 
magneaium or manganese. 

Zead-saU. ^^When a boiling dilute solution of the ammonia-salt is 

poured into a boiling dilute solution of neutral acetate of lead, there is 

immediately formea an orange-yellow precipitate of the |-- basic salt 

containing 87 p. o. lead-ozide; and the liquid decanted therefrom after 

VOL. ;ki. p 



210 BENZENE: NITKOCHLORINB-NUCLEUS C^XOW. 

some seconds, forms palo yellow silky needles of the bibasic salt, wbicb 
give off y-3 p.c. (2 At.) water in vacuo at 100^ and contain 440 p. c. 
lead-oxide. — In solutions not too dilute, the ammonia- salt forms with 
lead-salts, a heavy, yellow, crystalline precipitate. 

The ammonia-salt forms with the salts of cadmium, cobalt, nickel and 
capper, on addition of ammonia, a precipitate which consiste of needle- 
shaped particles, scarcely soluble in ammonia. 

With nitrate of silver, the ammonia-salt forms a yellow translucent 
precipitate, and in case of great dilution, it gradually forms tenacious 

threads. 

The acid dissolves pretty easily in boiling alcohol, separating out on 

cooling, and more easily in etKer. (Laurent.) 



NUrochlorine-nudeua C^XCPH". 

Nitrobichlorocarbolic Acid. 

C"NCl»HH)» = C«XCPH»,0». 

Latobnt & Dblbos. (1845.) JV. Ann. Chim. Phy$. 19, 380; also 
J. pr, Ckem, 40, 382; abstr. Compt rend. 21, 1419. 

NiirobichloroearboUaure, Acide phinique nitrohichlori. 

Chlorine gas is passed through that portion of coal-tar oil which 
boils between 180° and 200°; a small quantity of water added; the 
liquid neutralised with ammonia, boiled with water, and filtered from the 
brown matter; the filtrate neutralised with nitric acid; and the crystals 
of nitrobichlorocarbolic acid which separate on cooling, purified by 
repeated recrystallisation from alcohoL 

Properties, Yellow oblique rhombic prisms. The acute lateral 
edges = 88°; angle between the base and a lateral face = 108° 20' to 30'. 



Cryttah 
12 C 


• 

72-0 
14-0 
70-8 
30 
48-0 


.... 34-65 
.... 6-74 
.... 34-07 
.... 1-44 
.... 23-10 


Laarent & Delbos. 
34-70 


N 

2 CI 


3300 


3 H 


1-55 


6 O 








CWNC1SH80« 


207-8 


.... 100-00 





The acid, when suddenly heated in a close yassel^ decomposes with 
fire. 

Easily soluble in water, 

Ammonia'Salt, — Aurora-red needles, which, when carefully heated, 
sublime partly nndecomposed. Contains 31 '2 p. c chlorine, and is there- 
fore C»XCPH»(NH*)0». 

Potash-salt. — Shining laminae, carmine-coloured or yellow by reflected 
light, according to the angle at which they are viewed. Contains 18*5 p. o. 
potash, therefore probably = C^»XCPKO>. 



TSRXITROCAKBOLIC ACID. 211 

The other salts likewise resemble the picrates- 

The acid dissolves with tolerable facility in alcohol and ether, and 
crystallises out on cooling. (Laurent and Delbos.) 



Binitrochlorobenzene. 

C"N»aH'0« = C"X«C1H». 

Laubbnt & Gbbhardt. Conipt chim. 1 849^ 4S9; abstr. 4f^n, JPfMrm. 
75, 79. 

BinUrochlorqphiniie, Binitrocklofjune, 

When binitrocarbolio acid is decomposed by pentachloride of phos- 
phorus, there is formed^ with evolution of hydrochloric acid and oxy- 
chloride of phosphorus^ a solution of excess of pentachloride of phosphorus 
in binitrochlorobenzene, which, when cold, may be decanted from the 
chloride of phosphorus which has crystallised out. — The compound is 
perhaps formed in this manner : 

c»x«H<02 + PCI* = c»x«aH» + pa»o» + hci. 

The yellowish oil which sinks to the bottom without dissolving, solidifies 
in a few days in the cirstalline form, and is washed with cold alcohol, 
which dissolves a small portion of it. The solution of the cr^rstals in 
hot alcohol becomes milky on cooling, and deposits a yellowish oil> which 
after a few hours solidifies in needles. (Laurent and Gerhardt.^ 



NUro^udeue C»X»H». 

Teniitrocarbolic or Picrio Acid. 

C^N'IPO" = C"X'H»,0» 

Havsmann. J, Fhys. 1788, Marz. 

Weltek. Ann. Chim, 29, 301 j also Scher, J. 3, 715. 

FouBCBOY <fc VAUauELiN. N, Gehl. 2,231. 

Chevbeul. Ann. Chim. 72, 113; also Gilh, 44, 150. 

MoBETTi. Brugn. Ohm. 17, 415; abo Sichw, 51, 69. 

Liebig. Schw. 49, 373, 51, 37 i. — Fogg. 13, in. — J^as^^Arch. 13,353; 

also Ann. Chim. Phys. 37, 286.— ulnw. Pharm, 9, S2. — Pogg. 

14, 466. 
W5HLEB. Pogg. 13, 488. 
Ddmas. Ann Chim. Phys. 53, 178; also Pogg. 29, 98; also Ann. Pharm. 

9, 80. — JSr. Ann. Chim. Phys. 2, 228; also Ann. Phann. 39, 350 ; 

also J. pr. Chem. 24, 215. 
E. ScHUNCK. Ann. Pharm. 39, 7; 65, 234. 
Laubent. N. Ann. Chim. Phys. 3, 221; also Ann. Pharm. 43, 219; also 

J. pr. Chem. 25, 424» 
R. F. Mabchand, J. pr. Chem* 23, 363; 26, 897; 32, 35; 44, 91. 

p 2 



212 BBNZBNE: NITRO-NUCLEUS C»«X«m 

Stenhovse. PhiL Mag. J. [3] 28, 440; also Ann. Fkarm. 57, 84; also 
J.pr. Chem. 39, 221 — Further: Phil. Mag. J. [4], 8, 36; Ann. 
Pkarm. 01, 307; J.pr. Chem. 62,464; Pharm. Centr. 1854, 619; 
Jahretber. 1854, 466. 

Artificial Indigo-bitter, ChevreuVs artificial Bitter with maaimmm qf Nitric 
acid, Welter't Bitter, Carbazotic acid, KoMeniticktaure, Kohletuticktlqfsaure 
T. liebig^, Nitropicric acid, PikritualpetersHure, Nitrophenitic acid, Chrywlepic 
acid (from aloes), Jaune amer de Welter, Jaune amer, Acide carbO'OZotique, Acide 
jrikrique of Dnmas, Ac. nitrophemnqne of Laurent Discovered by Hausmann 

in 1788; examined with regard to its composition, by Liebig, Damas 

& Laurent 

Formation. 1. By the action of heated nitric acid on carbolic, 
terbromocirbolic and binitrocarbolic acid (Laurent), on saligenin, sali- 
cylous acid, salicin (Piria)^ salicylic acid, nitrosalicylic acid, phlorizin 
(Marchand), extract of willow-barK (Bottger & Will), indigo (Hausmann), 
cumarin (Delalande), aloes (Schunck), benzoin (E. Kopp), resin from 
Botany Bay, resio of Peru balsam (Stenhouse), and silk. (Welter.) 

Myrrh, quinine, morphine, and narcottne do not yield the acid (Liebig); whether it 
is contained in the yellow bitter substance into which albumin, fibrin, the crystalline 
lens, casein, and gluten, are converted by nitric acid, remains to be determined. • - 
2. By boiling temitranisol (C"X'H*0') with potash-ley. (Cahours.) 

Preparation. I. From Carbolic acid. The brown resinons masses 
precipitated during the preparation of binitrocarbolic acid (p. 206), are 
united with the mass obtained by precipitating with nitric acid the 
mother-liquors of binitrocarbolate of ammonia obtained in the same 
process; the united mass heated to the boiling point in a basin with com- 
mercial nitric acid; the acid liquid decanted after cooling; the residue 
washed with a small quantity of cold water, and boiled with very dilute 
ammonia; the filtrate repeatedly evaporated to the crystallising point; the 
resulting picrate of ammonia purified by crystallisation from boiling alcohol; 
and the beautiful needles of this salt treated with nitric acid to separate 
the picric acid, the quantity of which, thus obtained, is greater as the 
quantity of binitrocarbolic acid was less. The impure binitrocarbolic 
acid may also be converted into picric acid by boiling it with nitric 
acid, and recrystallising from alcohol the portion which separates out. 
(Laurent.) 

II. From Salicin. This substance treated with nitric acid yields 
remarkably pure picric acid, whereas phlorizin yields much less picric 
than phloretic acid. (Marchand.) 

III. From Indigo. 12 to 13 pts. of nitric acid of sp. gr. 1*43 are 
heated nearly to the boiling point m a capacious glass flask; 1 pt. of the 
best East Indian indigo in coarse powder, added in small portions, each 
addition being made as soon as the last portion has disappeared; the red- 
brown liquid concentrated by boiling till it becomes thick ish and lighter 
in colour; 3 pts. morid nitric acid added in case the liquid still gives off 
nitrous acid, and the boiling repeated : the mother-liquor decanted 
from the hard yellow, translucent crystals which form on cooling; these 
crystals washed with cold water and dissolved in a sufficient quantity of 
boiling water; the oily drops of artificial tannin which then rise to the 
surface removed with filtering paper; the solution filtered and lefi to 
cool; the yellow shining lamiu» of picric acid which separate removed 



PICRIC ACID. 213 

from the mother- Hqnor^ again dissolved in boiling Tvater, and neatralised 
with carbonate of potash j and the potash-salt which separates on cooling 
purified by repeated crystallisation, then dissolved In boiling water, and 
the liqnid mixed with sulphuric, hydrochloric or nitric acid, whereupon 
the picric acid crystallises out on cooliug. A large quantity of the potash- 
salt, requiring however further purification, may also be obtained from 
the first mother-liquor by precipitating therefrom a lar^e quantity of 
brown matter by addition of water, then dissolving it in ooiling water, 
uentralising with carbonate of potash, and cooling. — 4 pts. of indigo 
yield 1 pt. of picric acid. — Sometimes the solution of indigo in nitric 
acid does not yield any crystals; it must tlien be evaporated down, mixed 
with water, and the acid separated from the brown precipitate as above. 
The liquid above the precipitate likewise yields picric acid, when evapo- 
rated, boiled with nitric acid, neutralised with potash, <bc (Liebig.) — 
Moretti nsed 14 pts. of nitric acid of sp. gr. 1*30 to 1 pt. of indigo, 
whereas Chevrenl used only 2 pts. nitric acid, and therefore obtained 
chiefly nitrosalioylic (iudigotic) acid, artificial indigo-resin, &c., mixed 
with only a small quantity of picric acid. If the indigo be boiled with 
12 pts. of nitric acid, not merely for a few, but for 30 hours, till in fact 
only traces of the indigo-resin at first produced, remain, red vapours are 
continually evolved and the greater part of the picric acid is destroyed, 
so that ultimately the product amounts to only -^j of the indigo. (Blumenau, 
Ann. FhaiTn, 67, 115.) 

IV. From the Yellow JRmn of Botany Bay, — The resin of Xanihyrrluea 
hastUis is dissolved in the requisite quantity of strong nitric acid, where- 
upon red vapours are evolved, with violent fro thing, and a dark-red solution 
formed which becomes deep yellow after boiling. This solution is evapo- 
rated over the water-bath; the remaining yellow crystalline mass, which, 
together with picric acid, contains small quantities of oxalic and nitro- 
benzoic acid, neutralised with potash; the picrate of potash purified by 
two crystallisations, and then treated with hydrochloric acid, whicn 
separates the picric acid, to be further purified by two crystallisations, 
and amounting to 50 per cent, of the resm used. (Stenhouse.) 

y. From Benzoin, 1 pt. of benzoin (from which the benzoic acid 
may be previously extracted by alkalis: Kopp, Stenhouse), is gently 
heated with 8 pts. of commercial nitric acid; the mixture distilled, with 
four times repeated cohobation, after the effervescence has ceased; and 
the liquid, after decantation from the resin, mixed with four times its bulk 
of water, filtered from the precipitated yellow powder, and neutralised 
while hot with carbonate of potash : it then yields crystals of picrate of 
potash on cooling. (E. Kopp, N, Ann, Chim. Phys, 13, 233.) 

VI. From SUh. — 1. When 1 part of silk is distilled, with frequent 
cohobation, with 6 pts. of nitric acid, a solution is obtained which, by 
evaporation and cooling, yields crystals of picric and oxalic acid. 
(Welter.) — 2. In this process, 12 pts. of nitric acid are used; the 
residue in the retort is neutralised with carbonate of potash; the crystals 
of picrate of potash purified by recrystallisation; and the acid precipi- 
tated from their solution by nitric acid. The product from silk is however 
much smaller than that which is obtained from indigo. (Liebig.) 

VII. From Aloes, 1. pt. of aloes is heated with 8 pts. of strong 
nitric acid till violent action takes place; the fire then removed; the 
mixture, after the gas-evolution has ceased, introduced into a retort; 
the greater part of the acid liquid poured off; the residue distilled with 
3 or 4 pts. of fresh nitric acid, which still causes a slow evolntion of 



214 BENZENE: NITRO-NUCLEUS C«Xm«. 

nitrio oxide, tiU the greater part of tbe nitric acid is decomposed or 
volatilised; the residue diluted with water, which separates the chry- 
sammic and aloetic acids still remaining undecomposed; the yellow- 
filtrate evaporated, in order to remove the greater part of the nitric acid; 
then neutralised with milk of lime; and pure picric acid precipitated from 
the filtrate by nitric acid. — Schunck formerly left the evaporated Uquid to crys- 
tallise; purified the crystals of picric acid from those of oxalic acid by careful washing 
with cold water; combined the remaining acid with potash; purified the salt by crystal- 
lisation, &c. ; and thereby obtained his Chrytolepic acid, which he regarded as isomeric, 
but not identical with picric acid. But the experiments of E. Robiquet, {N, J. Pharm. 
13, 44; 14. 179), of R. F. Marchand, {J.pr. Chem. 44. 91), of Mulder (J. pr. Chem. 
46, 1), and of Schunck himself (Ann, Pharm. 65, 234) soon led to the conclusion 
that the supposed peculiar characteristics of chrysolepic acid were due to small quanti- 
ties of admixed chrysammic or aloetic acid. 

Vltl. From Temitranisol. Temitranisol is boiled for a few minutes 
with moderately strong potash; water added till all the resulting potash- 
salt is dissolved; the salt allowed to crystallise by cooling; and the acid 
separated therefrom by boiling dilute nitric acid : it then separates on 
cooling in yellow shining needles, and may be purified by washing with 
cold water and crjrstalTisation from boiling water. (Canours, N. AntL 
Chim. Fky$. 25, 26; also J. pr, Chem, 46, 337). 

[Cahours regards this acid, called Picraninc aeid, as isomeric but not identical 
with picric acid, inasmuch as it exhibits differences in the crystalline form and fusibility, 
as also in its appearance and in the solubility of some of its salts. Till however these 
peculiarities are more clearly made out, and shown to be not merely accidental, the acid 
ma^ be regarded as picric acid. All statements respecting picric acid cited from 
Cahours rebite to this picraninc acid, and those of Schunck to the actd obtained from 
alocB.I 

Properties, Light yellow, strongly shining laminsB. (Liebig.) Yel- 
lowish octohedrons, often very much truncated on two of their summits 
(Welter); Jrellowish white needles and granules (Chevreul.) Crystalline 
system, the right prismatic; Fig, 66 without the feces y and m and those 
between e and a; a : «' = 128** 36'; w : < = 115° 42' (115° 30', 
according to Laurent); a: a — 109° 50' (108°; ^ : a = 125°: Laurent, 
Bev, sclent, 9, 24); a :u= 125° 5' , a : a behind = 111° 57' (Mitscherlich, 
Fogg, 13,375). — The acid from indigo crystallises from hot water in 
lemon-yellow, opaque laminae, which become yelh)wish brown and trans- 
parent in warm air, crystallise from alcohol in transparent yellowish 
brown laminss, and from ether in transparent yellowish brown prisms, 
which become lemon-yellow and dull on exposure to the air, but recover 
their original appearance when strongly breathed upon. (Blumenan.)— • 
Chrysolepic acid; golden-yellow shining scales. (Schunck.) — Picranisie 
acid: small hard, highly lustrous prisms. (Cahours.) — The acid melts 
(Liebig) when slowly heated, forming a brownish yellow oil, which 
solidifies in a crystalline mass on cooling. (Schunck.) When slightly 
heated in contact with the air, it volatilises undecomposed (Liebig, 
Welter); at a higher temperature, it boils and gives off a thick, yellow, 
suffocating, irritating, and intensely bitter vapour (Schunck), and sublimes 
in small yellowish white needles and scales (Fouroroy A Vauquelin, 
Chevreul), or passes over as a brown liquid which crystallises on cooling. 
(Schunck.) — It tastes very bitter and somewhat harsh and sour, and 
reddens litmus. (Fourcroy & Vauquelin, Chevreul, Liebig.) The impure 
acid from indigo in doses of 1 to 10 grains, kills rabbits and dogs with 
delirium and convulsions. (Rapp, Eapp et Fohr, Diss, de efectib, venen^ 
mat. am. Waltheri; Tub. 1821.) 



PICRIC ACID. 215 

Laurent, Marchand^ 
from carbolic acid, from aaliein, Jrom salicylic acid. 

12 C 72 .... 31-44 31-82 31-34 31-38 

3 N 42 .... 18-34 18-62 18-51 18-60 

3H 3 .... 1-31 1-41 1'57 1-54 

14 O 112 .... 48-91 48-15 48*58 48-48 



C13N8HK)". 229 .... 100-00 lOO'OO 100-00 10000 



Liebigy Dumas, Erdmann & 

from Indigo, from Indigo, Marchand, 

earlier. later, earlier. later. from Indigo. 

C... 31-92 .... 35-04 31*8 .... 31-88 31-45 

N 14-99 .... 1618 18-5 .... 18-50 18-49 

H .... 1-4 .... 1-45 1-37 

53-09 .... 48-78 483 .... 48-17 48-69 

100-00 .... 10000 100-0 .... 10000 100-00 



Slenhouse, Schunck, Malder, Cahours, 

^tafw'Bmf -^^^ ^toe*. from Aloe: Jrom T^mHranisol. 

C 31-53 .... 32-12 .... 31-4 31-29 ^ 

N 18-60 ... 180 18-40 

H 1-42 .... 1-41 .... 1-4 1-31 

O 47-87 .... 49-2 49-00 

100-00 .... 1000 100-00 

Liebig alveays found a certain qnantlty of H^ which he formerly regarded aa unes* 
aential, but {Ann, Pkarm. Si 82), estimated at 1*10 p.c. 

The crystallised acid mixed with 5 times its weight of lead-oxide and 
with water, and dried, nltimatelj in vacuo at 100°, gives off 3*6 p. c. 
water (1 At. amounts to 3'.93 p. c. Laurent), 1 At. water is also set free 
when the acid combines with potash, soda, or oxide of silver. (Marchand.) 

DecompoBitioiu. 1. The acid, when quickly Jieated in a retort, melts 
(boils violently, according to Shunck) and blackens with explosion, and 
then takes fire, giving off nitrogen, nitric oxide, nitrons acid, water, 
carbonic acid, hydrocyanic and a combustible gas (depositing a large 
quantity of soot, according to Schunck), and leaves charcoal. (Chevreul.) — 
2. When qnickly heated in contact with the air, both the melting acid 
and its vapour take fire and burn with a yellow, very smoky flame (Liebig), 
and leave a small quantity of charcoal. (Schunck.) 

3. When chlorine gas is passed for several days through the aqueous 
acid, or when the acid is distilled with aqueous chloride of lime, which 
then becomes heated and deposits carbonate of lime, — or with chlorate of 
potash and hydrochloric acid, the picric acid is resolved into chloropicrin 
which distils over, and chloranil, the greater part of which remains 
behind. Boiling aqua-regia acts in a similar manner, excepting that it 
produces more chloropicrin and less chloranil. (Stenhonse, Fhil. Mag. J, 
33, 53; also Ann. Fharm., 66, 241; Hofmann, Ann, Pharm, 52, 02.) — 
In a similar manner, picric acid is resolved, by heating with bromine and 
water, into bromopicrin and bromanil. (p. 217.) — It is also converted 



216 BENZENE : NITRO-NUCLBUS C>»X»H». 

into bromopicrin by distillation with hypobromite of lime. (Stenhonse, 

Phil. Mag. J, [4], 8^ 36.) Chlorine gas does not decompose the acid (not even 
in the melted state ; Sehunci)^ neither does melted iodine (or bromine : Marchand), or 
chlorine water, chloride of gold, or hydrochloric acid, even at the boiling heat ; even 
, boiling aqua-regia scarcely acts upon it, (Liebig.) But nitric acid boiled with it for 
several days, appears under certain circumstances to exert a decomposing action, 
(Blumenaa.) 



We may here insert, as an appendix, the description of chloropicrin and bromo- 
picrin, which have been discovered since the publication of the portion of this Handbook 
relating to the 2*carbon compounds. 



Chloropicrin. C^NCPO* = CXCl*. 

Stenhouse. (1848.) FhU. Mag. J. [3], 33, 53; also Ann. JPharm. 
66^241; hlso J, pr, Chem. 45> 5G. — Gerhardt and Cahoars. Compt 
Chim. 1849, 34 and 170. 

Formation. 1. By tbe distillation of picric acid, styphnic acid or 
chrysammic acid with chloride of lime and water. Hence also when the 
bodies which yield either of these three acids by treatment with nitric 
acid, are first boiled with nitric acid and then distilled with chloride of 
lime. To these belong : Creosote, salicin, indigo, cumai'in^ the yellow 
resin of Botany Bay, liquid storax, benzoin, rera-balsam, galbanum, 
gum asafoBtida, guni-ammoniacum, purree, aloes, extract of Campeachy 
wood, log-wood, fustic, red sandal-wood, &c. Lastly, Dammara resin, 
and the chlorinated resin formed in the decomposition of usnic acid by 
chlorine, likewise yield chloropicrin when treated with nitric acid and 
chloride of lime. — 2. By treating picric acid with chlorine-water or 
aqua-regia, or a mixture of chlorate of potash and hydrochloric acid. 
(Stenhouse.) 

Freparaiion, Aqueous picric acid is distilled with chloride of lime, 
till, after about a quarter of an hour*s boiling, no more heavy oil passes 
over with tho water. Should the residue be still yellow, it must be redis- 
tilled with fresh chloride of lime. The oil is separated from the watery 
distillate, washed with water to which a little carbonate of magnesia 
has been added, dried by placing it over chloride of calcium, and 
rectified. (Stenhouse.) 

Properties. Transparent, colourless oil, of sp. gr. 1-6657; refracts 
light strongly; boils at 120°. Its odour, in the dilute state, is peculiarly 
aromatic, but in the concentrated state very sharp, and attacks the nose 
and eyes, less persistently, but quite as violently, as volatile chloride of 
cyanogen and oil of mustard. It is neutral to vegetable colours, 
(iStenhouse.) 



Calculation, 
2 C 


according to Gerbardt. 
12-0 7*31 


N 


14-0 8-52 


3 CI 


106-2 64-68 


4 


32-0 1Q-4Q 




COCCI" 


164-2 100-00 



PICRIC ACID. 217 

Calcolation according to Stenhouse. Stenhonse. Cahonrs. 

4 C 240 .... 6-32 658 .... 7-14 

2N 280 .... 7-37 7C8 

7 01 247-8 .... 65-25 64 79 .... 64-43 

10 O 80-0 .... 21-06 20-73 

H 0-22 

379-8 .... 100-00 100-00 

Deeompositians* 1 . Chloropicrin sastains, without alteration^ a heat 
of 150^; bat when passed throagh a red-hot tiibe^ it is completely decom- 
posed, yielding nitric oxide, chlorine, and sesqaichloride of carbon. -— 
2. It is not decomposed, eren hy prolonged contact with aqneons potash, 
hot gradually bj alcoholic potash, with separation of chloride of potas- 
siam and nitrate of potash. — 8. Aqneons ammonia exerts scarcely any 
action upon chloropicrin; butammoniacal gas or alcoholic ammonia produces 
sal-ammoniac and nitrate of ammonia. — 4. A small piece of potassium 
gently heated in the oil, causes strong explosion; at ordinary tempera- 
tures, it produces in a few days chloride of potassium and nitre. — Sul- 
phuric, nitric, and hydrochloric acid do not act upon it, even at a boiling 
heat. (Stenhonse.) 

Comhinatums. Chloropicrin dissolves very sparingly in water, but 
with great facility in alcohol and ether. — (Stenhonse.) 



t. Bromopicrin. O»NBr»0* = (?XBr». 

Stenhouse. Phil. Mag. J, [4], 8, 36; Ann, Pkarm, 01, 307; J.pr. 
Chem. 62, 464; Pkarm. Centr. 1854, 619; Jahresber, 1854, 466. 

Formation, (p, 216.) 

Preparation, — 1« Picric acid is distilled with a solution of hypobro- 
mite of lime, and the product washed with aqneons carbonate of soda> 
shaken up with mercury to remove free bromine, and dehydrated by 
digestion (not distillation) with chloride of calcium, which does not 
dissolve in it. — 2. When picric acid is digested for some hours with 
bromine and water, bromopicrin is obtained of a yellow colour arising 
from the presence of free bromine, which may be removed as above; but 
the product is still impure, probably containing a bromide of carbon G'fii^, 
produced by the continued action of bromine on the bromopicrin. 

Properties, ^-Treptaed by (1) : Colourless liquid, heavier than water, 
and smelling verv much like chloropicrin; its vapour attacks the eyes 
very strongly. Soiling point above 100^ 

Stenhoiue. 

(1.) (2.) 

2 C M 12 .... 4-03 

N 14 .... 4-66 

3 Br 240 .... 8054 .... 80-015 .... 85-3 

4 O 32 .... 10-77 

CXBr* 298 .... 100-00 

Tbc excess io the analysis (2) is probably due to the presence of CBr*. (vid, tup,) 

Bromopicrin may be heated nearly to its boiling noint without altera- 
tion; but when it begins to boil, it is decomposed, with evolution of 



218 BENZENE: NITRO-NUCLEUS C»X»H.» 

brown-red vapours, even in an atmoepbere of carbonic acid. At a higher 
temperature^ it is decomposed, with slight explosion. 

Dissolves very sparingly in water, but readily in alcohol and ether. 
The alcoholic solution is not immediately precipitated by nitrate of 
silver, but after some time, in the cold, and immediately on the applica- 
tion of heat^ bromide of silver is precipitated. (Stenhouse.) % 



4. Picric acid gently heated with peroxide of manganese and sulphurio 
acid, becomes hot and gives off nitrous vapours. (Wohler.) 

5. Picric acid boiled with strong potash-ley in excess is decomposed 
(according to Dumas, Ann, Chim. Fhyt, 58, 186, with abundant evolution 
of ammonia), and an opaque brown solution formed, from which boiling 
alcohol extracts a yellow needle-shaped salt, which decolorises tincture of 
indigo when boiled with it in presence of sulphuric acid. (Wohler.)-^ 
When picric acid is mixed with excess of baryta- water and the liquid 
boiled down to dryness, the residual mass, which is at first yellowish red, 
becomes brownish yellow; gives off when boiled down with fresh water, a 
large quantity of ammonia; and the residue, if then exhausted by boiling 
with water (while the mass on the filter contains no more picric acid, but 
evolves a large quantity of prussic acid when treated w*ith hydrochloric 
acid) yields a pale yellow filtrate, which is free from picric acid, but con- 
tains free baryta, cyanide of barium, and a yellowish amorphous salt 
which gives off nitric acid when acted upon by oil of vitriol. (Wohler.) 

6. Picric acid digested, as in tlie cold indigo- vat, with protosulphate 
of iron, excess of hydrate of lime or baryta, and water, yields a brown 
red mass; and the resulting brown red filtrate, when freed by carbonic 
acid from excess of alkali, and then filtered and evaporated, leaves a 
black-brown amorphous compound of deoxidised picric acid with lime or 
Intryta, which dissolves readily and with blood-red colour in water, 
deflagrates like gunpowder when heated, evolving hydrocyanate of 
ammonia, and leaves, first a tumefied charcoal, then an alkaline carbonate. 
When the aqueous solution of the barium-compound is precipitated by 
neutral acetate of lead and a small quantity of ammonia (to ensure com- 
plete precipitation), the lead-compound is obtained in the form of a 
thick, red-brown precipitate, which explodes by heat as strongly as the 
lime or baryta-salts, and dissolves sparingly in water, forming a deep 
yellow solution. By suspending the lead-precipitate in water, decom- 
posing it with sulphuretted hydrogen, frequently exhausting the sulphide 
of lead with boiling water, and evaporating the dark yellow filtrate, 
deoxidised picric acid (nitrohcematic acid) is obtained in brown crystal- 
line grains. This acid, when subjected to dry distillation, melts, exhibits 
a kind of detonation, but without fire, gives off a large quantity of hydro- 
cyanate of ammonia, and leaves a shining charcoal which burns away 
without residue. The acid dissolves with some difficulty in water, forming 
a yellow solution. With aqueous solutions of the alkalis, it forms bitter, 
deep blood-red solutions; and paper moistened with the acid and held over 
ammonia, becomes as red as if it were moistened with ferric sulphocyanide. 
The solution of the acid leaves on evaporation, a brown mass, with traces 
of crystals, which explodes when heated, with emission of fire and a large 
quantity of hydrocyanate of ammonia (evolving ammonia when treated 
with potash), and from whose concentrated solution hydrochloric acid 
throws down the deoxidised picric acid in the pulverulent form. Thiq 



PICRIC ACID. 219 

acid cannot be reconverted into picric acid by the action of nitric acid. 
(Wbhler.) The bright blood-red colour which picric acid and its salts 
prodnce with ferrous sulphate and excess of aqueous alkali, affords 
a means of detecting traces of it. (E. Kopp, J^, Ann. Chim. Phys, 
13, 285.) — According to B. Pugh {Ann, Pharm. 96, 85), picric acid 
treated with a very large excess of ferrous sulphate, and subsequently 
with an alkali, yields a colourless filtrate, which, on addition of an 
acid, assumes a deep blue colour, gradually passing by boiling or 
by contact with the air, into purple, yellow, and dingy brown. — 
%, When sulphuretted hydrogen is passed to saturation through an 
alcoholic solution of picric acid saturated in the cold and neutralised with 
ammonia, the liquid assumes an intense red colour and yields dark red 
crystals of the ammonia-salt of picramic (or nitroheematic) acid, 
C^'X^AdH'O^ The formation of this acid is represented by the 
equation : 

C«(N0*)«H30» + 6HS = C«(NCH)«(NH2)HS02 + 4130 + 63. 

On distilling off the alcohol from the liquid, sulphur is deposited, and 
an additional crop of crystals of the ammonia-salt obtained. (A. Girard, 
Compt rend, 36, 421; Ann, Fharm, 88, 281.) — The identity of nitro- 
biematic with picramic acid was suggested by Gerhardt {TraitS de Chim, 
org, 3, 46), and has since been established by E. Pugh {Ann, Pharm, 
96, 83), and by the further experiments of Girard. {Compt rend, 42, 59.) 
The formation of picramic acid by the action of protosalts of iron on 
picric acid, as in Wohler's process, is expressed by the equation : 

C«(NO*)»H»0» + 12FeO + 2HO = C»(NO*)«(NH2)H»0« + 6Fe»0». 

Protochloride of iron and protochloride of tin act in the same manner as 
the protosulphate of iron; a similar product, together with a large quan- 
tity of dark brown matter, is also formed by the action of zinc on aqueous 
picric acid. Cuprous oxide does not appear to exert any reducing action 
upon picric acid. (Pugh.) Picric acid is also converted into picramic 
acid by the action of ferrous acetate, the sulphides of the alkali-metals, 
nascent hydrogen, and cuprous chloride. No reducing agent appears 
capable of removing more than 1 At. NO* from picric acid. (Girard.) •[[. 
— 7. By boiling with sulphite of ammonia, picric acid is decomposed 
in the same manner as nitronaphthalin. (Piria.) — 8. Picric acid takes 
fire and burns vividly when slightly heated with phosphorus and potas- 
sium. (Wohler.) It detonates moderately, but with vivid emission of 
light, when struck in contact with sodium. 

Pentachloride of phosphorus acts violently on picric acid, forming 
Moropkryl, C"X'H«C1 : (Pisani, Compt rend. 39, 852.) 

C»X8H»0» + PC1» = Ci3X»H«Ci + Pa»03 + HCl. 

Comhinations, — Picric acid (also the acid from aloes) dissolves at 5^ 
in 160 pts. of water, at 15° in 86, at 20° in 81, at 225° in 77, at 26'' in 
73, and at 77° in 26 pts. (Marchand.) The solution has a brighter 
yellow colour than the acid itself. (Liebig.) From the cold-saturated 
solution, an equal measure of oil of vitriol throws down the greater part 
of the acid, e,g, •{- from a solution saturated at 22*5°. (Marchand.) 

The acid is insoluble in cold, but dissolves in hot oil of vitriol, and is 
precipitated in its original state on dilution with water. (Liebig.) — It 
dissolves abundantly in nitric add (Schunck), and even in the fuming 
ncid at a boiling heat without docomposition. (Cahours.) 



220 BENZENE : NITRO NUCLEUS C»«xni». 

The Picrates^ Temitrocarbolatn^ or Nitrophenuates, are neairal and 
crjstallisablei have a bitter taste, and mostly a yellow colour. They 
detonate wbea heated (at the melting point of lead, and more violently 
than the binitrocarbolates : Laurent), or at least deflagrato, like gun- 
powder; the detonation is strongest in close vessels, and those salts whoso 
base contains the oxygen in the least intimate state of combination, 
exhibit the weakest detonation. Picrate cf potash or baryta boated to 
redness with a large quantity of chloride of potassium, yields nitrogen 
and carbonic acid, but no carbonic oxide. (Liebig.) 

Picrate of Ammoniay — Eight-sided prisms belonging to the right 
prismatic system, and with four-sided summits. Fig, 66, without y-£E^e8 
and without the faces between a and t: u:u z=. 69°; u:m = 145° 30'; 
a :a = 135°; a above : a below =. 115°. (Laurent, Hev. tcient 9, 26.) 
Small yellow, bitter scales^ which scarcely detonate when heated. 
(Hatchett, N, Gehl, 1, 369.) Long narrow laminie having a light yellow 
colour and strong lustre. When gently heated in a glass tube, they 
volatilise completely in inflammable vapours; when suddenly heated, they 
bum without explosion, and leave a large quantity of charcoal. They 
dissolve readily in water, with difficulty in alcohol. (Liebig.) — The yellow 
crystals when gently heated, melt, give off their ammonia, and then yield 
a sublimate of the acid; when suddenly heated, they deflagrate with a 
hissing noise. (Marchand.) Aqueous picric acid added to ammoniacal 
salts, throws down a copious precipitate of picrate of ammonia. (H. Hose, 

■P^^'- 49, 186.) — Chryiolepate qf ammonia: Dark brown needles (Schanck); 
PicrarUwie : Sometimes orange-yellow, sometimes aiirora»red needles. (Ca]K>ui«.) 



Dumas. Marchand. 



Cabonrs. 
pellow. red. 

12 C 72 .... 29'27 293 .... 29-47 .... 29-30 .... 29*35 

4N 56 .... 22-76 23*2 .... 22-40 .... 22*86 .... 2289 

6 H 6 .... 2*44 2-6 .... 2*49 .... 2-49 .... 2*45 

14 112 .... 45-53 44*9 .... 45-64 .... 45'35 .... 45-31 

C"X»H«(NH<)0« 246 .... 100-00 100-0 .... 10000 .... 100-00 .... 100-00 

Picrate of Potash, — Obtained by neutralising with potash a solution 
of the acid in hot water, — or, according to Liebig, in the state of 
greatest purity, by digesting an aqueous solution of chloride of potassium 
with mercurous picrate, then filtering and cooling. Orange-yellow 
neutral needles. (Welter, Chevreul.) Yellow, highly lustrous, opaque, 
four-sided needles, several inches long; when obtamed from a dilute 
solution, they appear by reflected light, sometimes red, sometimes green. 
(Liebig.) The form of the needles is that of Fig. 54 elongated, gene- 
rally with t' and m-faccs; u:u' = 70**; » : i* = 139° nearly. (Laurent; 
comp* Miller. Pogg, 36, 478.)— - The salt assumes an aurora-red tint every 
time it is heated, but without altering in weight. (Laurent) It explodes 
like gunpowder, difi'using a resinous smoke (Welter); it likewise deto- 
nates under the hammer, emitting at the same time a reddish white light. 
(Fourcroy and Vauqnelin.) Heated in a glass tube, it detonates violently, 
yielding soot and hydrocyanic acid (Chevreul); it melts when heated in 
a glass tube, and explodes immediately afterwards with a tremendous 
report, shattering the tube and leaving a small residue of charcoaL 
(Liebig.) Chlorine deprives the solution of its yellow colour and renders 
it milky. (Welter.) Hydrochloric or nitriQ ^cid, added to a solutjion <;^ 



ACRIC ACID. 221 

the salt in warm water, abstracts the potash, so that the picric acid 
crystallises on cooling (Welter); but on evaporating the mixture, the 
hydrochloric or nitric acid volatilises, and picrate of potash is left. 
(Chevrenl.) An alcoholic solution of picric acid also throws down picrate 
of potash after a while from an aqueous solution of nitre. (Liebig.) The 
salt requires at least 260 pts. of water at 15° to dissolve it (Liebig), but 
dissolves in 14 pt& of boiling water (Chevreul); the solution saturated 
while hot, solidifies on cooling into a mass composed of needles. (Liebig.) 
It is insoluble in alcohol. (Liebig.) — Chrytolepate of potash t Needles and 
laminBy yellowish brown by transmitted, violet and with metallic lustre by reflected 
light (Schanck.) Pierankate qf potash : Chestnut-brown needles with a golden lostre. 
(Cahonrs.) 

CrjfiiaU. Dumas. ^ mJ^cS. Schnnclc 

12 C 72-0 .... 26-95 .... 26*7 .... 2730 .... 2741 

3 N 420 .... 15-72 .... .... 1570 .... 1587 

2 H 2-0 .... 0-75 .... 1-1 .... 0-81 .... 1*02 

KO 47-2 .... 17-66 .... 16-9 .... 1725 .... 17-56 

13 O 1040 .... 38-92 .... .... 38*94 .... 38-14 

C«NSH«KO" 267-2 .... 10000 10000 .... 10000 

Liebig estimated the amount of potash in the crystals at 16*21, Laurent at 17*41, 
Stenhonse at 17*68, and Cahonrs at 17*65 p. c. 

Picrate of Soda. ^'Slender, yellow, shining needles, which behave 
like the potash-salt, and dissolve in 10 to 14 pts. of water at 15°. 
(Liebig.) They contain 1238 p. c. soda and no water of crystallisation, 
and detonate with some violence when heated. (Marchand.) — Pic?*a- 
niiote of soda: golden-yellow needles, much more soluble than the potash- 
salt. (Cahonrs.) 

Picrate of Baryta. — a. Bibasic. — 1. When the salt b is heated to 
d50°— 370^ for 14 hours, and exhausted with water, the salt a remains 
on the filter in the form of a dark brown powder which explodes with 
extreme violence at 500° to 600°, and contains 40*7 p. c. baryta. — 
2. When the salt 6 is boiled for some time with weak baryta- water, 
a precipitate is formed consisting of the salt a mixed with carbonate 
of baryta; the greater portion of the salt b however remains in the 
filtrate undecomposed. (Marchand.) 

b. Monobasic. — Separates from the solution of carbonate of baryta 
in the aqueous acid in hard, dark yellow, four-sided prisms and broad 
laminsa. They give off 12*5 p. o. water of crystallisation at 100°. They 
melt when heated and explode violently, especially if the heat be gradu- 
ally raised, emitting at tne same time a very dazzling yellowish flame. 
They dissolve readily in water: chloride of potassium added to the solution 
forms in a few minutes a precipitate of picrate of potash. (Liebig.^ The 
crystals are oblique rectangular prisms, which give off 10*0 p. c. (4 At.) 
water in vacuo at ordinary temperatures, and the whole, amounting to 
15*6 p.c. (6 At.) at 150°. (Laurent.) The prisms give off 10-62 p. a 
at 100° to 120°, and 11-16 p. o. altogether at 350°, at which temperature 
however, a portion of the acid goes off together with the water, and on 
dissolving the residue in water, a small quantity of the salt a remains. 



222 BENZENE: NITRO-NUCLEUS C»X»H>. 

(Marcfaand.) — Pieranitate qf baryta : Golden yellow needles, baTiog a niky lustre, 
sparingly soluble, and containing 25*41 p. c. baryta. (Cahours.) 



Crjf»taU, Liebig. Laurent. Marchand. 

20*99 



12 C 

3 N 


720 

42-0 


.... ai-08 
.... 12-30 


7 H 


7-0 


.... 2-05 


18 


76-6 

144-0 


.... 22-42 
.... 4215 



217 
20-87 .... 21-66 .... 22-27 



C"N»H2BaO" + 5Aq.... 341-6 .... 10000 

PicrateofStr<mtia.^~'Hwd, yellow, shinbig c]y0tai& They ^ve off 
11*29 p. c. (4 At) water at 150°^ then yield a sablimate of the aoid, and 
leave a mixture of a monobasic salt, and a brown bibasic salt containing 
31*93 p. c. strontia, which detonates with great yiolence. The monobasio 
salt detonates sharply, and in the dark with a dazzling purple flame. It 
dissolves easily in cold, very easily in boiling water, and very slowly in 
boiling absolute alcohol, which renders the crystals tnrbid by extracting 
water from them. — Pierani$ate qf Strowtia: Yellow, sparingly soiable, slender 
needles, having a silky lustre. (Cahonrs.) 

Cry9taU. Mardiand* 

C"N>H«0« 220 .... 69-40 

SrO 52 .... 16-40 16*43 

5 HO 45 .... 14*20 

C"N»H8SrO" + 5Aq .... 317 .... 100*00 

Picrate of Lime, — Obtained by dissolving carbonate of lime in the 
aqueous acid. Smooth four-sidea prisms, which detonate when heated 
like the potash-salt, and dissolve readily in water. (Liebig.) The 
crystals -contain 9*56 p. c. lime, and therefore 5 At. water. When 
moderately heated, they likewise yield a basic salt They dissolve in 
water even more readily than the baryta or the strontia-salt. (Marchand.) 

Picrate of MagnedoL--^ Very long, slender, flat needles of a light 
yellow colour, detonating very strongly when heated (after giving oft 
water, according to Mardumd), easily soluble in water. (Liebig.) They 
appear to contam 5 At. water. They dissolve in water atill more readily 
than the lime-salt, but are nearly insoluble in boiling alcohol which 
abstracts their water of crystallisation. (Marchand.) 

Picric acid forms white scales with bydrochlorate of alumina and with tartar" 
emetic. (Moretti.) 

PiorcUe of Manganese. — The brown crystals appears to contain 8 At. 
water, 3 At. of which escape rapidly in the air, so that the air-dried salt 
contains 11 '8 p. c. protoxide of manganese and 5 At. water, 4 At. of 
which it gives off at 130°. (Marchand.) 

DHed at 130^. Mardiaod. 

12 C 72 .... 27*17 27*19 

3 N 42 .... 15-86 

3 U 3 .... 1*13 1*40 

MnO 36 .... 13-59 13*50 

14 O 112 .... 42-26 



C»N5H«MnO" + Aq .... 265 .... 10000 



PICRIC ACID, 92.3 

Ficrate of Zinc, — The beautiful yellow transparent crystals belonging 
to the right prismatic system^ which effloresce quickly, give off 8*0 p. c. 
(3 At.) water in dry air, 9*3 p. c. altogether at 100^, and 17'24 p. o. 
altogether (nearly 7 At.) at 140°, at which temperature however, a small 
quantity of acid likewise goes off; and leave a salt which contains 14-33 
p. c. zinc-oxide, therefore still retains 1 At. water, and when more strongly 
heated, swells up, gives off water and acid, and finally detonates mode- 
rately bnt with a bright flame. In the flame of a candle, the salt takes 
fire, flying about quickly in fiery flakes, and giving off a thick black 
smoke. The salt dried at 140'', melts in boiling water to a brown liquid, 
which when stirred about, absorbs water and solidifies in a yellow crys- 
talline mass. The salt dissolves abundantly in alcohol, and on subse- 
quent evaporation, forms a thick syrup, which when agitated in the cold, 
solidifies to a mass of needles. (Marchand.) 



12 


Dried 


in vacuo, 
72*0 


MM £0'09 •• 

.... 13-76 
.... 2-30 .. 
.... 13-17 .. 
.... 47-18 


Marchanl. 
23-30 


3N 




42-0 




7 H 




7-0 


2-52 


ZnO . 
18 O 




40-2 

144-0 


13-57 











C»N5H2ZnO" + 5Aq.. 3052 ..., 10000 

Picrate of Lead. — a. Quintohasic. — Formed by precipitating a boiling 
dilute solution of neutral acetate of lead with picrate of ammonia strongly 
supersaturated with ammonia. The dark yellow powder, when examined 
by the microscope, appears to consist of rectangular tables, mixed however 
with a few colourless crystals. (Laurent.) When heated, it burns 
without detonation, but with projection, and leaves suboxide of lead, 
which changes to protoxide on exposure to the air. (Marchand.) 



12 C 

3 N 


72 

42 


.... 9-23 

.... d*«)D 

0-26 
.... 71-80 

.... LA «j«j 


Lanrent. 

.... 

Z 69-67 


Marchand at 100^ 


2 H 


2 


""^ 0-52 


5PbO. 
13 O... 


560 

104 


70-92 


4PbO + 


Ci2N8HJpbO» 780 


.... 100-00 







h. Terhasic. — a. Anhydrotis, — From a solution of neutral acetate of 
lead mixed with a little ammonia, a concentrated solution of picrate of 
potash throws down during ebullition, a yellowish red crystalline powder, 
which is nearly insoluble in water even at the boiling heat, does not give 
off quite 1 p. c. water at 130°, and detonates with violence at a stronger 
heat, as also under the hammer. (Marchand.) 

p. HydrcUed. — A mixture of picrate of ammonia and slightly 
acidulated acetate of lead yields on addition of ammonia, a light yellow 
precipitate, which crystallises on standing in small shining scales unctuous 
to the touch, which detonate at 200"^, and with difiiculty by percussion. 
(Marchand.) To this place belongs perhaps the precipitate which Laurent obtained 

in yellow strongly detonating flakes by mixing picrate of ammonia with basic acetate 
of lead. 



224 BENZENE: NtTRO-NUCLSUS C»X>HS. 



12 C 

3 N 


a. 


at 130 


72 

42 

2 

336 

104 


•••• 
•••• 

•••• 
•••• 


12*95 

7-55 

0-36 

60-43 .. 
18-71 


Marchand. 


2 H 








3 PdO •«»«••• 






59-64 


13 O 




!•«■■•■•»•• 




2PbO,C»N»H«PbO".. 

p. at IOC 
12 C 


556 

)\ 

72 

42 

5 

336 

128 


•••• 

•••• 
•••• 
••■• 

•••■ 


100-00 

12*35 .. 

7-20 

0-86 .. 
57-63 .. 
21-96 


Marchand. 
12-73 


3 N 








e u 






0-81 


3 PbO 






57-20 


16 O 


•■•■••••• 







2PO,C»«N»H2PbOi* + 3Aq 583 ....100-00 

Marchand distinguishes also a light yellow ■{•basic salt containing 52*33 p.c. 
(5 At) oxide and 6*51 (8 At.) water, which detonates violently even at 180". 

e, Bihatic. — 1. A boiling dilute mixture of picrate of ammonia and 
neutral acetate of lead deposits at first heavy crystals of the salt c, then 
lighter, p«ile yellow, shining laminsB of a sesquibasic salt [or perhaps of 
the salt containing acetic acid] which may for the most part be separated 
by elutriatiou. Dark yellow microscopic rhombic tables which giro off 
1*6 p. c. water at 100°,and detonate with violence when struck. ^Laurent) 
-»2. When neutral acetate of lead is precipitated in the cold oy picrate 
of ammonia, yellow, shining, micaceous scales are obtained which 
detonate violently when struck or heated. (Marchand.) 

Air-'dritd, 

C"N»H»OM 220 ..., 

2 PbO 224 .... 

HO 9 .... 





Laurent. 


Marchand. 


48-56 






49-45 ... 


45-07 .. 


49*48 


1-99 ... 


1-60 





PbO,C>*N»H«PbO" + Aq 453 .... 100*00 
The deficiency in the lead-oxide arose firom admixture of the lighter salt. (Laurent) 

d. Honobarie,'^ The hot mixture of an alkaline picrate and slightly 
acidulated acetate of lead [not in excess f], yields on cooling, brown 
needles which detonate with violence and dissolve pretty easily in water. 
(E. Kopp, J^. Ann. Chim, Phys. 13, 233.) Aqueous picric acid satu- 
rated while hot with carbonate of lead, yields detonating needles sparingly 
soluble in water. (Chevreul.) 

Needlet, E. Kopp. 

C«N«HK>a 220 .... 64-51 6470 

PbO 112 .... 32-85 32-76 

HO 9 .... 2*64 2-54 

C"N»H«PbO" ■»• Aq .... 341 .... 10000 100-00 

Pieraeetate of Lead, — The hot aqueous mixture of picrate of potash 
and excess of acetate of lead yields on cooling, and by further evapo- 
ration and cooling of the mother-liquor, light yellow, highly lustrous 



PICRIC ACID. 225 

rliombio Iamin». The ciystalB bare an acid reactioiii esdiale nearly all 
tbe aeetic^aoid even at ordinary temperatures after drying, and are cou* 
Terted into a yellow nearly insoluble powder containing scarcely any 
acetic acid, wbereas tbey previously dissolved with ^Ekcility. ^E. Robiquet, 
iV. J, Pliarm. 14^ 179.) They give off 4-37 p.c. water (ana acetic acid) 
at 1$0°, and when treated with sulphuric acid, evolve acetic acid. 
(Marchand.) Their aqueous solution is resolved by evaporation into 
yellow, pulverulent picrate of lead (which dissoWes in a large quantity 
of boiling water and likewise in acetate of lead), and crystaUises there* 
from in laroinsB, and acetate of lead which remains in solution. (Schunck, 
Marchand.) If the acetic acid be replaced as it evaporates during the 
boiling down of the solution, the residue when tolerably concentrated, 
yields brown scales having a metallic lustre, and probably consisting of 
neutral picrate of lead. (Schunck.) 

The pale yellow, shining laminae obtained by Laurent (p. 244 )« which were doubtless 
identical with this salt, but in which he did not look for acetic acid, g:iTe off 3' 6 p. c. 
water in Tacuo at 110% contain 42'08 p. c. lead -oxide, and detonate by percussion. 

Schnnck, Marchand^ Robiqnet, 



16 


Dried. 


96 

42 

5 

224 

128 


.... 19*40 

.... o*4tl 

.... 101 
.... 45-25 
.... 25-85 


a<100«. 

.... 17-42 
.... 8-64 
.... 1-07 
.... 47-56 
.... 25-31 


.... 


at 180^ 
18-33 

1-34 
45-88 


by time. 
.... 20-82 


3N , 




7-32 


5 H 




1-12 


2PbO 

16 O 




.... 40-76 
29-98 


C"N»H»PbO»* + 


C<H»PbO* .... 


495 


.... 100-00 


.... 100-00 






100-00 



If the recent crystals contained 2 At. water, they would give off 3-51 p. c in 
drying. According to Schnnck, the dry salt is 3PbO,2Ci<N'HK>» -f PbO,C«HH>' ; 
according to Marchand, the same + 4Aq; according to Robiquet, about 
24PbO,C»N»H«0",3C*H»0». 

From aqueous chloride of iron, picric acid throws down white scales 
(Moretti); it does not redden ferric salts. (Liebig.) 

Picrate of CobaU. — By dissolving carbonate of cobalt in the boiling 
aqueous acid, evaporating, dissolving the dry residue in boiling absolute 
alcohol, and recrystallising from water tbe crystals whicb separate from 
the filtrate, dark brown needles are obtained, whicb melt and give off the 
wbole of their water of crystallisation, amounting to 1 4*4 p. c. (5 At.) 
between 100'^ and 110°, and at a stronger heat, decompose suddenly with 
a hissing noise and a dazzling white light, the mass being scattered about 
in all direction& (Marchand.) 

CryetaU,^ Marchand. 

12 C 72-0 .... 23-80 24-46 

3N 42-0 .... 13-88 

7 H 7-0 .... 2-32 2-66 

CoO 37-5 .... 12-40 1217 

18 O 1440 .... 47-60 

C»N»H2CoO" + 5Aq.. 302-5 .... 10000 

Picrate of Nichd.'-^k solution of carbonate of nickel in tbe acid, 
abandoned to spontaneous evaporation, deposits in the middle of the basin, 

VOL. XI. Q 



226 BSNZENE: NITRO-NUCLBUS C»=XSH». 

greea transpardnt fihining crystals exhibiting a dichroisin similar to tbat 
of aranic salts, and at the edge, brown dendritic efflorescences. The 
green crystals, which contain 8 At. water, quickly effloresce on exposure 
to the air, and are converted into the brown salt (containing 6 At water); 
over oil of vitriol they soon give off 7 '6 p. c. (3 At.) water. The same 
brown salt separates from the alcoholic solution on evaporation, in dark 
brown crystals which yield a light brown powder. It giyes off at 130^ 
11 '72 p. c. (4 At.) water, and between 160'' and 130°, water con- 
taining acid, melting at the same time and being converted into a basic 
salt, which at a stronger heat, explodes with some violence and with a 
dazzling white flama The salt dissolves easily in water and alcohol, and 
the alcoholic solution, when rapidly evaporated to dryness, leaves a 
greenish brown varnish, which forms a brown crystalline mass with 
a comparatively small quantity, and a green crystolline mass with a 
larger quantity of water. (Marchand.) 

Dried at 100''. Marchand. 

12 C 720 .... 27-02 27-30 

3N 42-0 .... 15-76 

3 H 30 .... 112 1-50 

NiO 37-6 .... 1407 1413 

14 O 1120 .... 42 03 

C"N»H«NiO" + Aq... 266-5 .... 100-00 

Ficrate of Copper, — By precipitating picrate of ^ryta with sul- 
phate of copper and evaporating the filtrate, green fern-like laminsB are 
obtained, which do not detonate or take ^re when heated, deliquesce in 
the air, and dissolve in 1 pt of water. (Liebig.) — 2. The greenish 
brown solution of carbonate of copper in the boiling acid leaves on evapo- 
ration a crystalline mixture of a basic salt, soluble in water but not in 
alcohol, and a neutral salt which may be dissolved out by boiling alcohol. 
This solution evaporated at a gentle heat to the crystallising point, yields 
small green shining needles, and a mother-liquor, which, after evapo- 
ration to a sprup, solidifies on being stirred. — The crystals effloresce in 
the air : they melt at 110°, givin^^ off 1 1*44 p. c. (3 At.) water, and form 
a brown mass, which at 150°, gives off 4 or 5 p. c. more water together 
with picric acid, so that it is afterwards mixed with a still more basic 
Fait. Finally, a slight explosion takes place, accompanied by a dark red 
flame and a large quantity of smoke containing nitrous acid, cyanogen, 
hydrocyanic acid, and perhaps also Boutin's cyanyl. (Marchand.) 



12 C 

3 N 


CryttaU, 


72 

42 

7 

40 

144 


.... 23-61 .. 
.... 13-77 

2-30 .. 

.... X«j* it •■ 

.... 47-21 


Mardiand. 
24-31 


f H 




2*50 


CuO 

18 O ......... 




13-29 



CWN»H«CuO" + 5Aq .... 305 .... 100-00 



Mercur<m$ PicraU. — Separates on cooling from a hot aqueous mixture 
of the potash-salt and mercurons nitrate, in small yellow four-sided prisms 
(according to Moretti, in white scales). Does not detonate when heated, 
but burns away like gunpowder. Requires more than 1200 pts. of cold 
water to di.psolve it. (Liebig.) 



PICKIC ACID. 227 

C12NM120" 220 .... 51-40 

Hg20 208 .... 48-60 46-21 



C»»N»H«Hg*OM 428 .... 100-00 

Mercuric Picrate. — By dissolving mercurio oxide in the aqueous acid, 
a compound ia obtained which detonates when heated. (Cherreul.) 

Ticrate of Silver, — The solution of oxide of silver in the aqueous 
acid, or a mixture of aqueous nitrate of silver with the acid or its potash- 
salt, is evaporated at a gentle heat and left to cool. Beautiful, yellow, 
shining needles united in radiated groups. (Chevreul, Liebig.) The salt 
blackens on exposure to the air (and light 1) and detonates when heated. 
(Chevreul.) When heated it burns without detonation, like gunpowder. 
Dissolves readily in water. (Liebig.) OhrygolepcUe of silver : — Brown- 
red needles (Schnnck); Ficranisate of nlvcr : Orange-yellow needles. 
(Cahours.) 

Duivas. Maccbapd. 

12 C 72 .... 21-43 21-35 

SN 42 .... 12-50 

2H 8 .... 0-60 0-97 

Ag 108 .... 32-14 31-80 .... 31*8 

14 112 .... 33-33 

C»-N«aUgO" .... 336 .... 100-00 

Hence, according to Laorent, the needles give off 2*2 to 3 p.c. at 100** in vacuo, 
and according to Marchand, they give up 3-1 p. c. ; these chemists suppose them to 
contain 1 At. water. 

Picric acid dissolves readily in alcohol and in ether. (Liebig, Schunck, 
Cahours.) 

It dissolves spari&gly in cold creouUCj but re^ abundantly in the same 
liquid when hot, forming a yellow solution from which it does not 
separate on cooling. (Reichenbach.) 

It precipitates gelatin. (Chevreul.) — It imparts a permanent yellow 
tinge to cloth-stuffs, Ac. T According to J. J. Pohl, (Wien, aJcad. Ber. 
9, 386), this character may serve to distinguish between animal and 
yegetable tissues, only the former being coloured yellow by picric acid . — 
The presence of picric acid in beer (in which it ia said to be sometimes 
introduced ns a substitute for hops) may be detected even to the amount 
of tflg^^ftfl, by boiling a piece of unbleached sheep's wool for 6 to 10 
minutes in the suspected liquid, and then washing it : if picric acid bo 
present, the wool assumes a canary-yellow colour. (Pohl, Wien, Akad. 
Ber. 12, 88.) % 



Picric Ether. 

A solution of picric acid in absolute alcohol mixed with a little oil of 
vitriol, is boiled for some hours in a flask having an ascending condensing 
tube attached to it, so that the alcohol may continually run back; and the 

Q 2 



228 BENZENE : NFTRO-NUCLBUS CifX>H>. 

liquid is mixed with ammonia^ and afterwards witli water which separates 

the ether. — Erdmann {J.pr, Chtm, 37, 413) did not lucoeed in preparing picric 
ether by this prooess. 

Yellowish laminsR, which melt at 91^ and boil with decomposition at 
800^ Inodorous, but has a burning bitter taste. 

Sparingly soluble in cold, more easily in boiling water. (Mitscherlich^ 
Lehrh, der ChenUe, 1,222; J.pr, Chem. 22, 195.) 

[This is the only instance yet known of the production of a compound 
ether from an acid aldide (containing 20 outside the nucleus) ]. 



%, Appendix to Picric Acid, 

Temitrocresylic Acid. 

When fuming nitric acid is added by small portions to creosote (con- 
taining C^^H'O*) in a vessel surrounded with ice, the colour of the liquid 
gradually changes to deep red, and after the addition of a rolume of 
nitric acid about equal to that of the creosote, the liquid separates 
into two layers, the upper of a deep red colour, the lower black and 
tarry. The upper portion neutralised with potash, solidified into a dis- 
tinctly crystalline mass sparingly soluble in cold but readily in hot water. 
(Pairlie, Chem. Sac. Qu. J. 7, 236.) 

Fairlie. 

CWN»H<OW 234-0 .... 8.S-25 

KO 47-2 .... 1675 17-08 

C"N»H*KO" 281-2 .... 100-00 

An attempt was made to obtain a substitution product eontaininf onlj 1 or 2 At. 
NO^ by acting with dilute nitric acid on an alcoholic solution of creosote preyionslj 
mixed with nitrate of urea ; but no definite result was obtained. (Fairlie.) ^. 



Styphnic Acid. 

C"N«H'0»« = C"X»H»,0*. 

CnETRBUL. Ann, Chim. 66, 216; 73, 43; the latter also in Gfilb, 44, 128. 

Erdmann. J, pr. Chem. 37, 409; 38, 355. 

R. BoTTGER and H. Will. Ann, Pharm, 58, 273. 

Fred. Rothe. J, pr. Chem, 46, 376. 

From vrd^voQ astringent. — Oxypierie acid (Erdmann); artificial bUter ot 
artificial tannin qf extract qf logwood. (Cherreul.)— First obtained in an impure 
state by Cherreul in 1808 ; in the pure state, and more precisely investigated, by 
Erdmann in 1846, and a few weeks later by BOttger & Will. 

Formation, By oontinued boiling of extract of logwood (Gheyrenl)i 
eaxanthone (Erdmann), gam-ammoniacam^ asafoBtida^ galbauunii aagape-' 



STTPHNIG ACID. 229 

num^ or tbe watery extract of fastio or sandal-wood (Bottger & Will), or 
peuoedanln (Rothe) with nitric acid. 

Pi'eparation* 1. From Aaqfceiida. 1 pi of asafoetida in lamps of 
the size of a walnut, is heated to a temperature between 70^ and 
75*^ in a wide porcelain basin^ with 4 to 6 pts. of nitric acid of 
ep. gr. 1% free from sulphuric and hydrochloric acid; and, after 
tbe resin has become soft and divided, and a thick froth has risen, — 
which must be prevented from running over by stirring — tbe mass, 
which is then lemon-coloured and viscid, is kept, togetber with tbe sur- 
rounding nitric acid liquid, at the boiling heat, with frequent addition of 
fresh acid, till (in 5 or 6 hours) it is completely dissolved; the dark 
red-brown solution, is then evaporated nearly to a syrup and mixed with a 
small quantity of water. If after this it gives a greasy resinous precipi- 
tate, it must be boiled for a longer time with nitric acia; but if it gives a 
yellowish sandy precipitate, it must be carefully evaporated to a thick syrup 
to drive off the greater part of the nitric acid; then heated to the boilingpoint 
with a tolerably large quantity of water; mixed with carbonate of potash 
as long as effervescence ensues, but no longer (so as not to redissolve any 
undecomposed portion of the resin which rises to the surface when the 
liquid is neutralised); strained through grey paper; evaporated, and left 
to crystallise. The mother-liouor repeatedly evaporated and cooled 
yields an additional quantity of crystals of impure styphnate of potash, 
till at last nitrate of potash (but no oxalate) separates out. The needle- 
shaped crystals, united in red-brown crusts and nodules, are freed from 
the mother-liquor by draining on bibulous paper; twice recrystallised 
from water, with audition of animal charcoal; then dissolved in the 
smallest possible quantity of boiling water; nitric acid added; and the 
styphnic acid, which separates after complete cooling as a yellowish white 
powder, or in fern-like laminae, collected on a filter, washed several times 
with cold water, and after thorough drying, recrystallised from boiling 
absolute alcohol The process yields 3 per cent, of styphnic acid. 
(Bottger <fe Will.) 

From commercial extixict of Logwood. 1 pt. of the extract is added 
to 4 or 6 pt& of nitric acid of sp. gr. 1 *37, heated to 40^ in a capacious 
dish; and as soon as the first violent action is over, the dark, red-brown 
liquid is continuously heated, with occasional addition of fresh acid, till 
the evaporated liquid, when mixed with water, begins to deposit styphnic 
acid in the form of a sandy powder. It is then left to cool; the mother- 
liquor decanted from the precipitated styphnic acid; this acid boiled with 
nitric acid, &c., &c., as long as styphnic acid can be obtained from it, 
and the product purified in the same manner as that obtained from asa- 
f(£tida. In this manner, 18*5 p.c. acid is obtained. (Bottger & Will.) 
— 1 pt of the extract is boiled to dryness with 5 pts. of nitric acid of 
32° Bm. and 2 pts. of water; the residue dissolved in boiling water; 
filtered hot from sand, &c.; and the flakes which fall down as the liquid 
cools, washed with cold water, dissolved in hot water, and filtered from the 
artificial orange -yellow resin. The acid is then obtained on cooling, in 
the form of a yellowish white, non-crystalline precipitate, still contami- 
nated with a small quantity of orange-yellow resin. (ChevreuL) 

Tbe artificial orange-yeUow resin of extract of logwood, the formation 
of which has just been described [which would probably be converted 
into styphnic acid by further boiling with nitric acid], is orange-yellow, 
sometimes granular, tastes slightly rough, does not redden litmus, becomes 



230 BENZENE: NITRO-NUCLEUS C^^'X'H*. 

charred on red-hot iron, and then deflagrates. It dissolves sparingly in 
cold water, more freely in hot water, forming a yellow solution which 
becomes turbid on cooling, is precipitated by sulphuric, hydrochloric or 
nitric acid, and by protochloride of tin^ acetate of lead, /erric sulphate 
(in red flakes) or nitrate of silrer, and immediately coagulates a solution 
of gelatin. (Chevreul.) 

3. Fi'om JSuxanthone cr BuxarUhic acid. These substances are boiled 
for some time with nitric acid of sp. gr. 1 '31 ; the solution evaporated 
over the water-bath, below 100° towards the end^ as otherwise the nitric 
acid would cpmpletely convert the styphnic acid into oxalic acid [in 
presence of hydrochloric acidt]; the sparingly soluble styphnic acid 
separated from the oxalic acid by repeated crystallisation, and dissolved 
in dilute carbonate of ammonia; this solution saturated while warm with 
carbonate of ammonia^ whereby the styphnate of ammonia, which is inso- 
luble in ac^ueous carbonate of ammonia, is made to crystallise in yellow 
four-sided prisms; these crystals, if too dark-coloured, purified by animal 
charcoal; and the styphnic acid separated from them by hydrochloric acid. 

4. From Peucedanin. The styphnic acid obtained by treating pence- 
danin with warm nitric acid, is mixed with potash to free it from the 
oxalic acid which is abundantly mixed with it; the styphnate of potash 
which crystallises out, washed with cold water; its solution in hot water 
precipitated by a lead-salt; and the acid separated from the precipitate. 
(Rothe-X 

Properties, Pale yellow^ regular, six-sided prisms having the habit 
of green lead ore; they grate between the teeth, melt when carefully 
heated, and solidify in the radiated form on cooling (Bottger & Will); 
pale, yellow or colourless needles or four-sided tables, which are fusible, 
sublime partly without decomposition, and likewise evaporate with the 
water when their aqueous solution is boiled (Erdmann); nearly colourless 
tables. (Rothe.) The acid has a slightly rough taste, neither bitter nor 
sour, but reddens litmus strongly, and wnen dissolved in alcohol, colours 
the skin permanently yellow (Bottger & Will); rough and leaving a 
persistent, irritating, and bitter after- taste. (Erdmann.) — Yellow, tastes 
somewhat sour, afterwards very rough and bitter. (Chevreul.) 

VrystaU. Bbttger & Will. Erdmann. 



12 C 


. 72 

. 42 

3 

. 128 


.... X / X^ • •»! 

«••• l'£o ...1 

.... 62-24 ... 


2915 ... 

16-97 ... 

1-55 ... 

62-33 ... 


29-62 


3 N 


17-3d 


3 H 


1-30 


16 O 


3!-78 


CBN^PO" ..., 


. ^45 


.... 10000 ... 


100-00 ... 


loo-bo 



The crystals do not give off inything between 100* and 150*. (Bdttger & Will.) 

Deeomposiiions. 1. The acid heated somewhat above its melting 
pointy gives off vapours which are set on fire by contact with a flaming 
Dody. When suddenly heated, it deflagrates like gunpowder, with a 
bright yellow flame, mostly bordered with orange-yellow. (Bott^r & 
Will.) Leaves a residue of charcoal. (Erdmann.) When gradually 
heated, it gives off nitrous gas, nitroeen, carbonic acid, inflammable gas 
and water, and leaves very finely-divided charcoal; on red-hot iron it 
deflagrates with flame. (Chevreul.) 2. It is completely destroyed by boiling 
nitro 'hydrochloric acid, with formation of oxalic acid> whereas boiling con- 



STYPHNIC ACID. 231 

ceuirated nitric or hydrochloric acid alone has no action upon it 
(B5ttger & Will.) — 3. It is decomposed bj boiling oil of vitriol. 
(Bottger & Will.) — It is not decomposed by boiling with excess of con- 
centrated potash; and when digested with lime and protosulphate of iron^ 
does not form a red liqaid as picric acid does, but a colourless liouid. 
(Erdmann.) — 4. It is not altered by sulphuretted hydrogen; but the light 
yellow mixture of the acid dissolved in alcohol with hydrosulphate of 
ammonia, immediately acquires a dark brown-red colour when heated^ 
and leaves on evaporation a black mass, containing, besides sulphur and a 
small quantity of black powder, an ammonia-salt which may be dissolved 
out by water, and whose acid resembles picric acid and.^stjrphnic acid. >— 
5. The hot aqueous acid dissolves protosulphide of iron with less evolu- 
tion of sulphuretted hydrogen than might be expected. With sine or 
iron, it likewise gives off a less than proportionate quantity of hydrogen, 
forming greenish brown solutions. It does not act on cadmium, lead, 
copper or silver. — Its powder strewn on potassium (not on sodium) 
takes fire when slightly pressed with a pestle. (Bottger & Will.) 

Combinations. The acid dissolves with yellow colour in 104 pts. 
of water at 25° (Erdmann), and iu 88 pts. at 62° (Bbttger & Will.) 

It dissolves abundantly in Birong nitric acidy less in Birong hydrochloric 
acid, and is partially precipitated from both acids by water in the form of 
a powder. (Bottger & Will.) ^ 

The acid easily decomposes carbonates. It takes up, for 1 At. HO, 
2 At. of base of the same or different kinds, forming bibasic simple and 
double salts which are neutral. (Bbttger & Will.) Nearly all gtyph- 
natei detonate, When subjected to a gradually increasing heat (not by 
percussion), even more violently than the piorates. (Bdttger and Will, 
Erdmann.) From the aqueous solutions of the heavy metallic salts of 
this acid, animal charcoal removes the whole of the oxide, especially 
from the stypb nates of manganese, lead, nickel and copper. (Bottger h 
Will, Rothe.) 

Styphnate of Ammonia. — a. Bihanc. The^'^treoosacid neutralised 
with ammonia (and then saturated, while warm, with solT^' e affaon ateumf 
ammonia, which diminishes the solubility of styphnate of ammonia in 
water : Erdmann), yields lar^e orange-yellow ni^edles (yellow four-sided 
prisms, according to Erdmann) which detonate slightly when heated, and 
dissolve in water more readily than the salt 6. 

Erdmann. Btf ttger & Will. Rothe. 
.... 25-81 26-89 .... 25*48 .... 2568 



12 C 


CryBtaU. 
72 


6N 


70 


9 H 


9 


16 O 


128 



2509 2509 .... 24-89 

3-23 3-22 .... 3-37 .... 341 

45-87 45-80 .... 4626 



NH»,CMN«H«(NH<)0". 279 .... 100-00 100-00 .... 10000 

&. Monohoiic. — Obtained by neutralising one-half of the acid with 
carbonate of ammonia, adding the other half, and then evaporating and 
cooling. A comparatively dilute solution yields large, light yellow, flat 
needles, and a solntion more concentrated by evaporation yields capillary 
interlaced needles, which detonate very slightly. (Bottger * Will.) 



234 BENZENE: NITRO-NUCLBUS C"X>Hs. 

SiyphnaU (tf Lead. — Quadrohanc. -~ The light jellow flakes preci- 
pitated bj the free acid from acetate of lead, detonate violently hy 
strong pressure and are scarcely soluble in water. (Bottger & Will.) 
The ammonia-salt forms a similar precipitate with acetate of lead in the 
cold, and small yellow needles from hot solutions. (Erdmann.) 

Jhied at 10€** Btfttger & Will. Erdmann. 

12 C 72 .... 10-26 10-32 

3 N 42 .... 5-98 

4 H 4 .... 0-37 0-G3 

4 PbO 448 .... 63-82 6368 .... 63*02 

17 O 136 .... 19-37 

3PbO,r>^Nni2PbO» + 2Aq.... 702 .... 100-00 

Ferrous Styphnate, — The filtrate obtained by precipitating the 
baryta-salt with ferrous sulphate^ slowly yields black-green crystals which 
dissolve readily and pass to a higher state of oxidation. (Bottger «& Will.) 

Ferric Styphnate. — The ammonia-salt mixed with iron-alum forms 
yellow needles. (Erdmann.) 

Styphnate of Cobalt, — The light brown^ violently detonating, and 
easily soluble needles united in nodules, give off 9*28 p. c. of water at 100°, 
and leave a salt containing 21*44 p. c. of protoxide of cobalt. (Bottger & 
Will.) 

Styphnate of Cobalt and Ammonium, — Brownish yellow needles. 
(Bottger k Will.) 

Styphnate of Cobalt and Potassium, — Hard brown crystalline 
nodules containing 11*7 p. c. oxide of cobalt, and not giving off any thing 
at 100°. (Bottger & Will.) 

Styphnate of Kickeh — Crystallises with difficulty in light yellow 
needles, which detonate with violence and dissolve very readily. 
(Bottger & Will.) 

Styphnate of Nickel and Potassium. — Brown cryslalline crusts. 
Detonates with tremendous violence when heated; contains 10*32 p. c. 
oxide of nickel^ and does not suffer any loss at 100^ (Bottger & Will.) 

Styphnate of Copper, — The evaporated dark brown solution of car- 
bonate of copper in the aqueous acid deposits, after a few days, long 
light green needles, which give off 13*81 p. c. f6 At.) water at 100°, and 
detonate with great violence at a stronger neat. (Bottger & Will.) 
Greyish yellow laminsd. (Erdmann.) 

BQttger & WUI. 

12 C 72 .... 21-56 21-90 

8N 42 .... 12-57 

4 H 4 .... 1-20 •. 1-57 

2 CuO 80 .... 23*95 2312 

17 O 136 .... 40-72 

CuO,C>aN»H«CaO»« + 2Aq.... 334 .... 10000 

Styphnate of. Copper and Anummium. — ObUined by dissolving 
oarbonate of copper in the saturated eolation of monobasic styphnate of 



CHLOROPICRTL. 235 

aminoni^ Short, thick> brown crjstals which give off 15*47 p. o. (6 At.) 
water at 100% deflagrate when heated^ anddissolrc with tolerable facility. 
(Bottger & Will.) 

JStyphnate of Copper and Fotatsium, — Prepared in like manner with 
the potash-ealt. Brown bard needled, generally grouped in nodules. Thejr 
give off 7*20 p. c. (3 At.) water at 100°, and detonate with tremendoiiB 
violence when strongly heated. (Bottger k Will) 



Dried at 100^ BSitger k WUl. 

CKNSH'O" ; 245-0 .... 73-75 

KO 47-2 .... 14-21 

CuO 40-0 .... 12-04 12-01 

CaO,Ci-N«H2ICO" + Aq... 832-2 .... 100-00 

StyphnaU ofSiher. — Bibasic. The solution of carbonate of silver in the 
aqueous acid at 60% or the mixture of the potash ^alt with a moderately 
strong solution of nitrate of silver prepared at 60° yields, when some- 
what quickly cooled, light yellow, flat needles, 3 inches long, or by slow 
cooling, laminae which dissolve sparingly in water, and from whose solu- 
tions, the silver is reduced on boiling with decomposition of the acid. 
(Bottger & Will) 



12 C 

3 N 


Dried at 100°. 

72 .... 

42 .... 


15-38 , 

8-98 

0-43 
49-57 , 
25-64 


Bottger & WUl. Erdmann. 
1504 

48-06 .... 50-50 .... 


Rothe. 


2 H 


2 .... 




2 AgO 

15 


232 .... 

120 .... 


50-25 



AgO,C»N»H«AgO»« ... 468 .... 10000 
Bottger Be Will Buppose the salt to contain 1 Aq in addition. 

Styphnio acid dissolves readily in alcohol and ether, and more readily 
in strong acetic acid than in water. (Bottger & Will.) 
It gives a copioas precipitate witn geUuin, (Chevreul.) 

Erdmann {J.pr. Chem, 37, 413) did not auooecd in preparing ttyphnit tther by 
heating ityphnic acid with alcohol and oil of yitriol. 



Ghloropicryl. 

C"N'H*C10» = C"X»tt»(Dl. 
Px8ANi* Oompt rend, 3D, S52} Ann., Fhqrm. 92, 826. 



236 BENZENE : AMIDOGEN-NUCLEUS C»AdH\ 

This oomponnd u obtained by tbe aetion of 1 At. penUMblorido of 
phosphoroB on 1 At. picrio acid^ oxjohloride of phoaplioros and hydro- 
oblorio acid being formed at the same time : 

c»x»H»o« + pa» - cwx«H«a + pa»o> + ho. 

The two bodies act Tiolently on each other at first, and oopions fames of 
hydrochloric acid are evolved. As soon as this action ceases, and the 
oxychloride of phosphorus begins to pass over, the retort mnst be removed 
from the fire, because the chloropicryl would be decomposed by further 
heating, and a resinous substance formed; hence the chloropicrvl cannot 
be completely purified from oxychloride of phosphorus by distillation. 

Yellow, solid body, having an agreeable odour. Water decomposes it, 
forming hydrochloric and picric acids. Carbonate of ammonia converts 
it into picramide (p. 245). It dissolves in alcohol and in ether. (Pisani.) 



4. Jmidogen^wleus (7'AdH*. 

Sulphophenylamide. 

C«NH^SH)* = C»AdH»^0*. 

Oerhardt & Chancel. Compt rend. Z5, 690. — Gbrhabdt & CaiozzA. 
Compi. rend, 37, 86. 

Azoture phenyUnffitreuM, Axoiure de SuffopMnyU et d'hydroghke. 

Formed by the action of ammonia on sulphite of chlorobenzene [or 
chloride of sulphophenyl C^H'S'OHU^p.lT*)]. It is most conveniently 
prepared by pouring the latter compound upon a large excess of pulverised 
carbonate of ammonia. The action begins immediately, and may be com- 
pleted by gently heating the mixture till the odour of the sulphate of 
chlorobenzene is no longer perceptible. The mass is then washed with 
cold water, to dissolve the hydrochlorate and carbonate of ammonia, and 
the residue crystallised from a small quantity of boiling alcohol. 

Splendid nacreous scales, insoluble in water, easily soluble in alcohol, 
soluble also in ammonia. 

CaleuhitUm* 

12 72 45-86 

N 14 8-92 

7H 7 4-46 

2 S 32 20*38 

4 O 32 20-38 



C»NIFS*0* 157 100-00 

Gerhardt regards this compound as the nitride of ndphaphenyl and 

rc«H»s»o* 

hydrogen = N< H , in other words, as ammonia in which 

I H 
1 At. H. is replaced by sulphophenyl, C'H'S'O'. By treating the con^ 



BITHIOBBNZOUC ACID*^ 237 

pound with yarions meiallio salts, of with the chlorides of organic 
radicals, one or more of the remaining atoms of hjdrogen may he 
replaced, e, g. 

Nitride of Sulphophenyl, Silver and Hydrogen^ C"NH*AgS*0*, or 



N^ H ,is 
_ 1 Ag 



ohtained in the form of a white crjsiaDine precipitate 



hy treating an alcoholic and ammoniacal solution of snlphophenylamide 
with nitrate of silver. 

Nitride of Sulphophenyl, Stdpkophenyl and Hydrogen, or Bistdphy 

pUnylamidey (?*NH"S*0* = N^ C«H»S»0* , is obtained in the crystalline 

form by gently heating the preceding silver-salt with chloride of snlpho- 
|henyl C"H*S»0*,C1 fsalphite of chlorobenzene, (p. 174)1, treating the 
product with ether, which dissolves out the new compound, and leaving 
the ether to evaporate. 

Similarly, by treating the snlphophenylamide with the chlorides of 
succinyl, C<H*0*C1, benzoyl C»*H*0»C1, and cumyl C^'H^O'CI, the 



{ C"HS«0* 
1 H 



compounds^ N < C^ H*0^ , ke, are ohtained. From these nitrides con- 



taining 2 At hydrogen replaced by organic radicals, silver-salts may be 

( C»HS*0* 
formed, such as N < 0® H^O^ ; and by treating such silver-salts with the 

chloride of an organic radical, a nitride may be formed containing three 
organic radicals, e,g. nitride of aulpkophenyl, benzoyl and cumyl, 

i C"H»S«0* 
N { C"H»0» (Gerhardt, Traite de Chimie orgmique, III, 75.) IT. 

( C*»H"0«. 



IT. Amtdogen-nuele^is C"Ad*H*. 

Biihiobenzolic Acid. 

C"N»H^S*0« = C"Ad»H*,4S0». 

L HiLKBNKAKP. Ann. Fharm. 95, 86. 
JHthiobenzoUe acid, PhenyldUutphodiamic acid. 

Formation, By the action of sulphite of ammonia on binitrobenzene 
(pp. 203, 205). 

The acid has not been ohtained in the free state. All its salts 
are soluble in water'; their general formula is C"N'H®M'S*0" or 
C"Ad*H«M»,4S0': the acid is therefore bibaaic. 

Bithiobenzolate of Ammonia. -— Preparation (p, 203). The needle-shaped 
crystals, i^ter being pressed between paper, form a yellowish mass, which 



2S8 BENZENE: AUIBOGBtf-NUGLBUS C>*AdBr*HO<. 

when purified bj wwlhing with alcohol and ether, fenns a perfectly white 
powder. 

Vrifd in vocM. KUkenkamp. 

12 C 72 .... 23-84 24-54 

4 N 56 .... 18-54 1820 

14 H 14 .... 4-64 4-88 

4S 64 .... 21-19 21-21 

12 O 96 .... 31-79 31-17 

C«N'H«(NH«;2,4SO» 302 .... 100-00 lOOOO 

The salt carbonises and intnmssces when heated, giving off snlpha- 
rous acid. Sulphnrio and hydrochloric acid, even when concentrated, do 
not act npon the salt in the cold; with the aid of heat, thej eliminate 
a pungent gas, but no sulphurous acid. Nitric acid acts in the same 
manner, but likewise colours the cold solution yellow. Chlorine forms a 
considerable quantity of cbloranil, together with traces of a brown 
resinous body. The salt dissolves very readily in water and aqueons 
alcohol, very sparingly soluble in absolute alcohol, and is insoluble in 
ether. The aqueous solution has an acid reaction. 

BUhiohenzolate of Baryta. — Obtained by adding the ammonia-salt to 
boiling baryta-water, continuing the ebullition as long as ammonia goos 
off, removing the excess of baryta by carbonic acid, evaporating the 
filtrate till a crystalline substance begins to separate, and then leaving 
it to slow evaporation. It then yields crystalline crusts, which may be 
purified by filtering from the mother-liquor and washing with alcohol. 
The salt is white with a slight tinge of red, insoluble in alcoliol anhy- 
drous and hydrated, also in ether. 



12 d 


Dried 


in vacuo. 
72*0 


.... 17-85 
.... 6-94 
.... 1-49 
... 34-04 . 
.... 15-87 ., 
.... 23-81 


Hilkenkemp. 


2N 




... 280 




6 H 




60 




2 Ba 




137-2 


* 33-73 . 


4S 




.... 640 


15-55 


12 O 




.... 96-0 












C»N^H«Ba«,4SO» .... 


.... 403-2 


.... 10000 





IT. Amidogen-nucUus C"AdBr»HO». 

Bromanilamic Acid. 

C«NBr»HK)« = C"AdBr»HO«,0\ 
Stenhousb. Fhil. Mag. J. [4], 8, 36; Ann. Pharm. 91, 313. 

The red-brown solution of bromanil (p. 172), in strong aqueous 
ammonia^ yields deiep brown-red needles of a salt which appears to be 
bromanilamate of ammonia; and by cautioosly adding sulphuric acid to the 



CHiORAmUMIO ACID* 289 

a^iie6ii8'aoliiiioii of tbigsalt, bromsiiiilainio acid is separaied in nearly 
blaek needles. If^ on the other band, the mixture is allowed to become 
heated, decolorisation takes place, and crystals separate haFiog exactly 
the appearance of bromanilio acid (p. 171). 



IT, Amidogetirnudeui C^Ad'Br'O*. 

Bromanilamide. 

C»N'Br»H*0* = C«Ad*Br»0»,0*. 
Stekhousb. JPkU. Mag. J. [4], 6^ 36; Ann, Pkarm. 01, 312. 

Obtained by passing dry ammoniacal gas into heated alcohol in which 
bromanil is suspended: also when bromanil is heated with alcohol and 
aqneons ammonia. The quantity of bromanilamide obtained by the 
latter method is however smaller, a larger portion of bromanilamate of 
ammonia, which is soluble in alcohol, being formed. 

Brown-red, crystalline powder, which sublimes, with partial decompo- 
sition, in brown crystals. It is nearly insoluble in water, alcohol, and 
ether. 

Stenhoose. 

12 C 72 .... 24-32 

2 N 28 .... 9-46 

2 Br laO .... 6406 64-21 

4 H 4 .... 1-35 

4 32 .... 10-81 

CWAtfBi^HH)* 296 .... 10000 

The specimen analysed was dissolved in alcohol contaming a little potash^ and 
precipitated by acetic aeid. (Steahoose.) H. 



Amidogen-nucleus C"AdCl*HO«. 

Chlorftnilamic Acid. 

C«NC1«H»0» = C»AdCPHO«,0*. 

Erdmann. (1841.) J. p'. Ghent. 22, 287. 

Laurent. iV. Ann. Ckim. Phys. 3,493. Rev. ment. 19, 141; abstr. 
J. pr. Chem. 36, 280. Compt. Chim. 1845, 173. 

ChlwanilamMdure, CMoranitam, Aeide ekloranOamigue. 

The blood-red solution of ohloranil in aqneons ammonia yields brown 
needles of chloranilammone : (chloranilamate of ammonia according to 
Laurent). (Erdmann, p. 198). 



240 BENZENE : AMIDOOBN NUCLEUS C»AdCPHO>. 

Preparation. 1. From tlie sataraied aqneons solution of these 
needles, after addition of sulphuric or hydrochloric aoid, the chlora- 
nilamic acid crystallises on cooling, in long hlack needles, which may he 
purified by pressure between paper, and crystallisation from the smallest 
possible quantity of boiling water. — Sometimes, especially when the 
addition of hydrochloric acid has produced too much heat, and the air 
Las acted on the mixture, a brown powder mixes with the needles and 
must be remored by recrystallisation. The chloranilamic acid which 
remains dissoWed in the acid mother-liquor of the needles, cannot be 
recovered by evaporation, which exerts a decomposing action, but may 
be obtained by extraction with ether and evaporation of the solvent. 
The mother-liquor of the chloranilammone yields a small extra quantity 
of chloranilamic acid, when treated with hydrochloric acid. — 2. The 
solution of chloranil in ammonia is supersaturated with hydrochloric acid, 
without previously separating the chloranilammone from the sal-ammoniac 
in the crystalline form, the mixture being constantly kept cool by cold 
water, and the crystals, which are scarcely contaminated with any brown 
powder, are purified by pressure between paper and recrystallisation 
from hot water. (Erdmann.) 

The violet powder of the black needles gives up its water at 100°; 
and becomes lighter in colour. (Erdmann.) 

Erdmann. Laurent. 

34*65 3508 .... 34*0 

6-73 7-40 

34-07 33-24 

1-45 1-75 .... 1-5 

23-10 22-53 



12 C 


Anhydrwu, 

79*0 


N 

2 CI 


14-0 . 

70-8 . 


3 H 


3-0 . 


6 


48-0 . 



C»NCPH»0« 207-8 .... 100-00 10000 

DecomposUums, 1. The needles, when heated in a test tube, appear to 
sublime undecomposed to a slight extent, but afterwards give off yellow 
and brown, litmus-reddening vapours, and leave a residue of charcoal. — « 
2. The aqueous solution mixed with snlphurio or hydrochloric acid 
remains unaltered in the cold or at a gentle heat, even after a considerable 
time; but on being heated to the boiling point, the violet mixture, if the 
air is completely excluded, gradually becomes light red, the more quickly 
the stronger the acid added, and immediately or on cooling deposits 
crystals of chloranilic acid, whilst an ammonia-salt remains in solution : 

C"NCPHH)« + 2H0 - C«CPH«0' + NH». 

Strong acetic acid does not exert any decomposing action, even with half 
an hour's boiling. »- The mixture of the acid with sulphuric or hydro- 
chloric acid, boiled in contact with the air, e,g» in a basin, becomes 
covered on cooling with an iridescent film, and deposits a brown powder 
together with a few laminss of chloranilamic acid. — 3. With aqueous 
potash, chloranilamic acid is resolved, even at 0°, into chloranilate of 
potash which crystallises, and ammonia which escapes. Also when heavy 
metallic salts are precipitated by chloranilamic acid or its ammonia-salt, 
more or less chloranilic acid appears to be produced, the salt of that acid 
fonuing at least a part of the precipitate. (Erdmann.) 

Combinations, EydraJted Chloranilamic add. — The above-mentioned 
black needles. They exhibit an adamantine lustre and yield a dark 



CtlLOIUNlLAMIC ACID. 241 

violet powder. Between 100° and 130°, thej ^ve off 18*92 p.o. (some- 
what more than 5 At.) water. Thej dissolve sparingly in water, forming 
a beautiful violet solution. (Erdmann.) 

ChloranUamate of Ammonia. — CMoranHammon. (Erdmann.) — The deep 
blood-red solution of chloranil in warm aqueous ammonia yields, partly on 
cooling, partly after careful evaporation, small, shining, chestnut-coloured 
needles, which must be freed from the mother-liquor by draining on 
paper. (Erdmann.) These crystals are produced immediately on mixing 
ammonia with chloranilamic acid* (Laurent.) 

Dehydrated at 120^ Erdmann. 

12 C 720 .... 82-03 33-06 

2N 28-0 .... 12-45 11-86 

2 CI 70-8 .... 31-49 31-62 

6H 60 .... 2-68 2-79 

6 48-0 .,.. 21-35 20-67 

C>K:i»Ad(NH<)0« 224-8 .... 100-00 100-00 

The crystals when dried give off 24*1 to 28 p.c (therefore probably 
8 At.) water. When heated in a test-tube, they yield a trace of violet 
sublimate, then a white sublimate, turning brown at the same time and 
becoming carbonised; heated on platinum-foil, they emit a purple smoke, 
and leave a difficultly combustible charcoal. The aqueous solution of the 
salt turns yellowish red when mixed with nitric acid, but does not 
deposit anything. Mixed with sulphuric or hydrochloric acid, it assumes 
a violet colour in the cold, becoming deeper at a moderate heat, and 
deposits black needles of chloranilamic acid, while a portion of that acid 
remains in solution, together with sulphate or hydrochlorate of ammonia 
and a certain quantity of chloranilic acid, into wnich moreover, the whole 
of the chloranilamic acid is converted by boiling, a brown powder being 
also formed if the air has access to the liquid, {vid, ntp.) Acetic acid does 
not decompose the salt. Cold potash slowly decomposes its aqueous 
solution, into chloranilate of potash which crystallises, and ammonia. — 
The salt dissolves in water^ especially when hot^ forming a purple solu- 
tion. (Erdmann.) 

The aqueous acid forms with chloride of barium a light brown preci- 
pitate, which dissolves with purple colour when the mixture is heated, 
out reappears on cooling in brown amorphous flakes, the liquid however 
retaining a reddish tint. (Erdmann.) 

Aqueous chloranilamic acid, as well as the ammonia-salt, forms with 
neutral acetate of lead, a red-brown precipitate; with ferric and nickel 
salts, a blackish cloud; with cupric sulphate, after a while, and with the 
acetate immediately, a greenish brown precipitate ; and with mercurous 
nitrate, a dark brown precipitate, whereas corrosive sublimate is not 
precipitated by ii (Erdmann.) 

The thick red-brown precipitate formed with nitrate of silver (the 
liquid, even when the silver-solution is in excess, retaining a deep violet 
colour, and depositing red-brown, often crystalline flakes when evapo- 
rated,) is decomposed by nitric acid, with formation of chloride of silver, 
and dissolves completely in hot water^ as well as in ammonia and acetic 
acid. (Erdmann.) 

VOL. XT. R 



242 



BENZENE: AMIDOGEN-NUCLEUS C»Ad«a*0«. 



The silver- salt varies in composition according to the mode of preparation : a. Pre- 
dpttated cold ; b. Precipitated warm ; c. The crystalline flakes deposited from the 
liquid filtered warm from b. The preparations were dried in each case at 130°. 
(Erdmann.) [Laurent appears to have precipitated his salt in the cold. It is probable that 
generally a mixture of diloranilate and chloranilamate of silver is produced, bat that 
the latter is more soluble in warm water, and is, therefore, for the most part, precipi- 
tated from warm mixtures on cooling in the form c] Brdmoun takes another view. 



12 C 72-0 

N 14-0 

2 CI 70-8 

2 H 20 

Ag 108-0 

6 O 48-0 

C^CPAdAgO«... 314-8 



22-87 
4*44 

22*49 
0-64 

34-31 

15-25 



a. 
21-50 

20-70 

0-57 

40-40 



5. 



e. 



17-90 ..,, 2M 

43-58 Z. 34-17 



Laurent. 

.... 21-80 
4-80 

0-62 



100*00 



AmidogenrnueUm C»Ad*Cl*0*. 

Chloranilamide. 

C"N«CPHK>* = C»Ad«Cl»Ol 
Laurent. (1845.) Bev. sclent 10, 141; abstr. J. pr. Chem. 36, 283. 

FormatUm. (p. 198.) 

Preparation, Chloranil dissolved in alcohol is ffently beaied with 
ammonia; the resulting dark red-brown precipitate freed from the alco- 
holic liquid, washed with alcohol, dissolved in gently heated alcohol 
containing potash, care being takeu not to heat too long or too strongly; 
the solution, filtered if necessary, neutralised while yet warm with acetic 
acid; and the quickly formed brown- red crystalline precipitate, collected 
on a filter, washed and dried. 

Properties. Dark carmine-coloured powder, consisting of fine needles 
and haying an almost metallic lustre. When carefully heated on a glass 
plate, it sublimes almost entirely in crystalline tufts, resting on a layer 
of charcoal. 



12 C. 
2N. 
2 CI 
4 H. 
4 0. 



72-0 
280 
70-8 
4-0 
320 



Laurent. 

34*82 35-2 

13-54 13-4 

34 21 34 

1 93 1-9 

15-47 15-5 



Ci^Nscra^O^ 206-8 .... 100-00 1000 

Decompositions. Chloranilamide boiled with potosh-ley, is resolved 
into ammonia, which escapes, and chloranilate of potash which crystallises: 

C»«N»C1«H^CH + 2K0 + 2H0 - C»C1=K=0« + 2NH». 



PICRAMIC ACm. 243 

It is not decompoeed hj boiling with aqneons or alcoholic hydro- 
chloric acid* 

CominnaUons. It diasolyes in water and in aqneons ammonia. 

Its riolet-red solntion in oil of vitriol is coloured blue hj a small 
quantity of water and wine-red by a larger quantity; and when treated 
with a still larger quantity, deposits a portion of the chloranilamide^ 
proTided the quantity of water and acid present is not too great. 

From its solntion in alcoholic potash, it is precipitated unaltered 
by adds. 

It is nearly insoluble in alcohol and ether* (Laurent.) 



% Amidoffen^ucleui C"X*AdIP. 

Picramic Acid. 

C»N»HK)" = C«X»AdH«,0». 

WoHLER. Pos^g. 13, 488. 

A. GiRARD. Compt rend, 36, 421; J. pr. Chem^ 59, 142. Ann, Pharm. 

88, 281; — further: Compt rend. 42, 59; J. pr. Chem, 67, 507. 
E. PuGH. Ann, Pharm, 96, 83; «7. pr. Chem, 65, 362. 

NUrohamatic acid, DecaddUed Picric acid. 

Formation and Preparation, (pp. 218, 219.; Girard'B method by the action of 
lulphuretted hydrogen appears to be tlie most prodnetlTe. 

Properties. The acid separated from its ammoniarsalt by acetic acid 
forms beautiful red needles, often grouped in tabular masses. (Girard); 
from an ethereal solution, it crystallises in distinct prismatic crystals with 
very acute terminal faces, garnet-coloured by reflected, yeUo wish-red by 
transmitted light (Pugh.) Has a slightly bitter taste (Girard); does 
not taste bitter. ^Pugh.l Melts at 165^, and solidifies in a crystalline 
mass on cooling. (Giraro.) 

» 

Crystal9. Girard (mean). 

12 C 72 .... sea ^....- 35-6 

SN 42 .... 21-1 21*4 

V Cl ....•• «••• 9 M.« ^*d ....M*- **0 

10 O 80 .... 40-3 #0-2 

C>2X»AdH»,0« . 199 .... 100-0 ........ 1«00 

Decompositions. 1. The acid heated above 165° is decomposed, with 
evolution of tarry vapours containing hydrocyanic acid and ammonia, 
and leaves a residue of charcoal. (Girard, Wohler, p. 218.) It burns 
vividly when thrown on red-hot coals. (Girard.) — 2. It dissolves at 
ordinary temperatures in sulphuric acid, forming a red solution, from 
which, on dilution with water and addition of ammonia, the picramic acid 
separates ont unaltered : similarly with hydrochloric acid; but by hot 

R 2 



244 BBNZGNB: AMIDOGEN-NUCLSUS C^XSAdHS. 

conceatrated snlphnrio acid it is decomposed and carbonised. (Qirard.) 
3. Strong nitric aoid decomposes it, with abundant evolution of nitrons 
fumes, the liquid assuming a straw-yellow colour and the picramic aoid 
being converted into picric aoid. (Girard, Pngh.) According to Wtfhler, 
nitroluBmatic acid is not reconyerted into picric add by the action of nitric acid (p. 218). 

OoTiibinatums. The acid dissolves with some difficulty in vfcUer, 
forming a yellow solution. ^Wohler.) It is nearly insoluble in water 
even at the boiling heat. (Qirard.) 

Picramic acid unites readily with hcues. Its salts are mostly crystalline; 
their general formula is C"X>AdH*M, 0^ 

Pieramate of Ammonia. — Preparation (p, 219) — Separates from the 
alcoholic solution by spontaneous evaporation, in dark oranc^red rhom- 
bohedral tables. Does not decompose at 1 00°, but at 1 35° it effloresces 
and gives off ammonia; melts at 165°, and decomposes at a higher tem* 
perature. It dissolves readily in water and alcohol, forming deep red 
solutions, but is insoluble in ether. The aqueous solution is decomposed 
by continued boiling, with separation of a brown powder. (Girard.) 



12 C 72 

4N 56 

8 H 8 


.... 33-33 
.... 25*93 .... 
.... 3-70 
.... S7-0i 


Girard. 
26-9 


10 O 80 




C»X2AdEP(NH*),0«. 216 


.... 100-00 





Pieramate of Potash. — Obtained by decomposing the hot solution of 
tiio ammonia-salt with potash. Separates on cooline; in red transparent 
elongated rhombic tables, containing 1 9-9 p. c. potash. Decomposes with 
slight detonation when somewhat strongly heated, and leaves a residue of 
charcoal. Dissolves pretty easily m water, sparingly in alcohol. 
(Giraid.) 

Girard. 

KO 47-2 .... 19-8 19-9 

C"N»H<0» 190-0 .... 80-2 

C»«X«AdHPK,0« .... 237-2 .... 1000 

Pieramate of Baryta, — On decomposing a hot solution of pieramate 
of ammonia with nitrate of baryta, this salt separates in small silky 
tufts of red and golden-yellow needles. It bears a heat of 200° without 
decomposition, but detonates at a higher temperature, leaving a residue of 
charcoal Dissolves sparingly in water and alcohol. Contains 27*9 p. o. 
baryta. (Girard.) 

Girard. 

BaO 76-6 .... 27-8 27-9 

C»«N»H*0« 190-0 .... 72-2 



CJ«X»AdH2Ba,0«.... 266-6 .... lOO'O 
The toloble picramates give no precipitate with &altf of mani^eneie. (Ginud.) 



c PICItAMmE. 215 

Pieramaie of Lead, — Oraoge-colonred powder which explodes when 
heated, and also by percussion^ but without much noise. Dissolves in 
water^ ammonia and acids, but is insoluble in alcohol. (Girard.) 

Solable picramates do not precipitate the salts of iron, cobalt^ or nickel, 

Picramate of Copper. — - Yellowish green, amorphous precipitate, which 
detonates slightly, is insoluble in water and alcohol, but soluble in acids. 
(Girard.) 

Girard* 

CuO 40 .... 17-3 ........ 17-2 

CMN»H*0» 190 .... 82-7 

CWX«AdH«Cii,0« 230 .... 100-0 

With mercuric salts, the soluble picramates form a red precipitate 
soluble in acids. 

Picramate of Silver. — Obtained by decomposing the ammonia-salt with 
nitrate of silver, in the form of a brick-red amorphous precipitate, which 
does not blacken by exposure to light, but decomposes, with blackening, 
at about 140°, leavmg a residue which melts at about 165°. On glowing 
coals, it bums without detonation. It is insoluble in cold water and in 
alcohol Boiling water decomposes it, leaving an insoluble residue. 
(Girard.) 

Girard. Pngh. 

AgO 116 .... 37-9 .... 37*3 .... 3775 

C"N»HW 190 .... 62-1 

C^XaAdH'Ag,^ 306 .... 100-0 



% Amdogenrnudeus = C"X'AdH*. 

Ficramide. 

C»N*HK)» = C"X»AdH» 
Pmani. Cmpt. rend. 39, 852; Ann. Pharm. 92, 326- 

Obtained by the action of ammonia on chloropicrvl (p. 236). When 
crude chloropicryl (containing oxychloride of phosphorus) « teiturateJ 
in the cold with excess of carbonate of ammoni^ and the maas treated 
with boiling water, a residue is obtained consistmg of picramide, which 
dissolves in boiling alcohol, and separat^ in crystalline pktes, dark 
yeUow by transmitted, violet by reflected light: its powder is light 
yellow. When heated, it decomposes without detonation, gmng off 
nitrous fumes, and leaving a carbonaceous residue. Heated with aqueous 
potash, it gives off ammonia and yields picrate of potash : 

[C»3X»(NHS)H» + KO,HO - C«XWK,0« + NH»]. 
Pissolvee sparingly in ether. (Pisani.) IF, 



246 benzbne: azo-nvcleus amvLK 



Aniline. 

0»NH' = C»NH»,H». 

Unybbdorben. (1826.) Pogg. 8, 397. 

RuKOB. Pogg. B\, 65 and 513; 32, 331. 

Fritzsche. J. pr. Chem. 30, 453; 27, 153; 28, 202. 

ZiNiN. J. pr. Chem. 27, 149; 36, 9H, 

A. W. HoPMAim. Ann. Pharm. 47, 31; 58, 8; 57, 265; 66, 129; 67, 61 

and 129; 70, 129; 74, 117; 75, 356. 
HoFHANN & MuspRATT. Ann. Pharm. 53, 221; 57, 210. 
Laurent. Gompt. rend, 17, 1366; also J. pr. Chem. 82, 286.*^^<?v. 

9cienlif. 18, 278 and 280; also J. pr. Chem. 36, 13. 
Qerhardt. N. J. Pharm. 9, 401; also N. Ann. Chim. Phys. 14, 1 17. — 

N. J. Pharm. 10, 5. 
Laurent & Gbrhardt. y. Ann. Chian. PhyB. 24, 163; also N. J^ Pharm. 

14, 130; aUo Ann. Pharm. 68, 15. 

KrftttMtm (UnTerdorben), JTymo/ (Range), Anilin (FHtxtoh*), Bentidam (Zinte), 
PMtuntid, Fkinylamme (Hofiaiaiiii), AmidopMmtte. 

Formation. 1. By heating carbolate of ammonia for some time by 
itself in a sealed tube: 

NH»,C"H«0» - VSW + 2H0. 

At 200^, only a trace of aniline is formed in half-«n-hour; bnt between 200* and 300*, 
a large quantity in the course of 18 days. (Laurent.) — 2. When nitrobenzene is 

decomposed by sulphuretted hydrogen in presence of alcohol and 
ammonia (Zinin, p. 672), or by zinc m presence of alcohol and hydro- 
chloric acid (Hofmann, p. 672), or by ferrous acetate; 

C»NH»0* + 12FeO + 2HO = 6Fe30« + CaNH'. 

Ferrous sulphate, oxalate and chloride, do not exert any action upon 
nitrobenzene. (A. Bechamp, N. Ann. Chim. Phys. 42, 186.) — 3. By 
distillation of azoxybenzene. (Zinin.) — 4. By distillation of anthranilio 
acid. (Fritzsche.) — 5. By passing the vapour of salicyhinlide, or nitro^ 
toluene, which is isomeric with it, over lime at a low red heat. (Hofmann 
and Muspratt.) Nitrometastyrol yields but a small quantity. (Hofinann & Blyth.) 
— 6. By distilling indigo per ee (Unverdorben), or with very strong 
potash-ley. (Fritzche.) — 7. In the dry distillation of coal, aniline passes 

over with the coal-tar. (Runge.) In the tar obtained by the diatiUatioa of 
animal sabatttioea, Hofinana did not fiad amlins ; AndersoB» however* fomid it ia tbfl 
product of tbe diatiUatioa of bones. 

Preparation. 1. From yi^robentene. — a. Nitrobenzene dissolvtd in 
alcohol is mixed with ammonia; sulphuretted hydrogen passed through 
the solution; the greater part of the alcohol gradually distilled, after a 
few days, from the liquid which contains crystals of sulphur, the liquid 
being cooled and decanted from the gradually deposited anlphur at oltei^ 



ANILINE. 247 

as it eaases percussive eballltion; and the distillation continued, after all 
the salphnr has separated, as long as the contents of the retort continue 
to deposit aniline in the form of a yellow oil at the bottom of the 
slightly alcoholic liquid: the oil thus deposited is afterwards rectified 
per te. (Zinin.) — b. Nitrobenzene dissolved in alcohol and distilled with 
an eqnaJ weight of hydrate of potash, is converted into azoxybenzene, 
which, by further distillation, is resolved into aniline, which passes over 
first and remains liquid, and azobenzene which passes over later and 
orystallises. The more volatile aniline is freed from the greater part of 
the azobenzene by fractional distillation, and dissolved in boiling dilute 
sulphuric acid; and the resulting solution, decanted from the azobenzene, 
which sinks to the bottom in the form of an oil, yields, on cooling, crystals 
of sulphate of aniline, which, when purified by recrystallisation and 
distilled with potash-ley, yield pure anihne. (Zinin.) T c. Nitrobenzene 
and ferrous acetate (3 pts. iron to 1 pt nitrobenzene) are mixed in a 
flask fitted with a distillation- tube to condense any acetate of aniline 
that may pass over, and heated in the water-bath; the contents of the 
flask then filtered (after being stirred up with water if too pasty); the 
residue on the filter washed with hot water; and the entire liquid dis- 
tilled: acetate of aniline and free acetic acid then paf«s over together with 
the watery vapours. The distillate is mixed with strong sulphuric acid 
(4 pts. acid to 10 pts. of nitrobenzene used) and the mixture distilled to 
expel the acetic acid; sulphate of aniline then remains and may be puri- 
fied by recrystallisation from alcohol, or immediately distilled with potash 
to separate the aniline. — When 1 pt. of nitrobenzene, l^pts. of pure 
iron-filings, and 1 pt of strong acetic acid, are introduced into a retort, a 
brisk action soon begins without external heating : 

C^H<i04 -I- 4ro •(- 2H0 » 2Fe^0^ •»- C^H'j 

and aniline, acetate of aniline, and a small quantity of undecomposed 
nitrobenzene collect in the receiver, which must be well cooled. The 
contents of the receiver are then poured back into the retort and distilled 
to dryness, and aqueous aniline separated from the distillate by caustic 
potash. (A. B6champ, N, Ann. Chivi. Pkys, 42, 186.) IT. 

2. From Indigo, — a. The oil obtained by the dry distillation of 
indigo is extracted by an acid. (Unverdorben.) — 6. Indigo-powder is 
introduced into highly concentrated potash-ley heated in a retort; the 
resulting brown mass neated as long as ammoniacal water and a browu 
oil pass over with strong intumescence: and the oil separated by distilla- 
tion into a brown resinous residue, and a colourless distillate of aniline^ 
amounting to 20 per cent, of the indigo. (Fritzsche.) 

3. From Coal-tar. — a. The tar is distilled till pitch remains behind; 
the pitch distilled with a quantity of sulphuric acid suflUcient to retain 
the greater part of the ammonia, the receiver being changed as soon as 
the distillate sinks in water; the oil which sinks in water, the heavy oil 
(the first portions of which contain a considerable quantity of aniline 
with but little leueol, while- the subsequent portions consist chiefiy of 
leucol), violently shaken in a carboy with strong commercial hydrochloric 
acid; this acid, after 24 hours* standing, separated by the siphon from 
exhausted oil floating on the surfistce, in order that it may be repeatedly 
treated with fresh oil, which may amount to 100 lbs. in all, and may take up 
a large quantity of bases; and the acid liquid strained through cloth or 
grey paper, mixed with milk of lime in a copper-still which must bo 
piimediately elo^ed^ and distilled over a strong fire, with good arrange- 



248 BENZENE: AZO-NUCLEUS C^NH*. 

ments for cooling. It then ^elds a first distillate consisting of a milky 
liqnid having an intoxicating odonr, and with brown-black oily drops 
floating on its surface; and afterwards^ when about half has passed over, 
and the odour of the distillate has become more agreeable and somewhat 
like that of bitter almonds, a second distillate, to be collected in a sepa- 
rate receiver, and consisting of a turbid watery liquid which holds but 
little oil in solution. The first distillate becomes clear when mixed with 
hydrochloric acid, and if mixed with potash after evaporation, deposits 
drops of an oil having an intoxicating odour, and consisting mainly of 
aniline and leucol, but containing also a small quantity of neutral oil. 
This oil does not dissolve completely in hydrochloric acid: hence, after 
removing the watery liquid, it must be dissolved in ether; shaken np 
with hydrochloric or snlphuric acid; and the liauid carefully separated 
from the ether, in which the neutral oil remains dissolved, and mixed in 
a tall cylindrical vessel with hydrate of potash or strong potash-ley, by 
which the basic oil is generally separated in the form of a lajrer which 
rises to the surface and may be removed with the pipette. If it should 
separate merely in fine drops which fill the entire liquid, they must be 
made to unite and rise to the surface, by mixing the liquid with common 
salt and setting it aside for several da3rs, and, if this method does not 
succeed, saturating the water with hydrate of potash; or else: the mix- 
ture may be distilled with water, whereupon the oil, amounting to ^rs ^^ 
the heavy coal-tar oil, collects in drops on the surface of the distillate. — 
a. The oily mixture of aniline and leucol thus obtained is distilled (to 
about f ) till a drop which passes over no longer turns blue with solution 
of chloride of lime; and the dark yellow distulate having an intoxicating 
odour, dehydrated by setting it aside for some days in contact with an 
equal quantity of hydrate of potash, then separated from the potash- 
solution by the pipette, and rapidly distilled in a current of dry hvdrogen, 
setting aside the first fourth which may contain water, and the last pale 
yellow portion which contains leucol. On redistilling the middle half, 
which is colourless, and again collecting apart the middle half of the 
distillate, aniline is obtained nearly pure, but still contaminated with a 
yery small quantity of a substance which has a penetrating ofiensive odour 
(Anderson's picoline), and makes it lighter than water. But by com- 
bining it with oxalic acid, purifying the oxalate of aniline by repeated 
crystallisation from alcohol, and distilling with potash, this odour may be 
entirely removed. — p. Or, the mixture of aniline and leucol is dissolved 
in absolute alcohol, neutralised with alcoholic oxalic acid, and the mother- 
liquor, which contains scarcely anything but oxalate of leucol, decanted, 
after standing for some hours, from the oxalate of aniline which separates 
in the form of a white crystalline mass. (Uofmann.) 

6. The oil obtained by distilling coal-tar over oxide of copper, is set 
aside for 8 hours with ^ pt. lime and 4 pts. water, the mixture being 
frequently shaken; the brownish yellow watery liquid filtered and dis- 
tilled to one-half; the distillate (consisting of a thick oil and a watery 
liquid, and containing carbolic acid, ammonia, aniline, leucol and pyrrhof) 
mixed with excess of hydrochloric acid, distilled to remove the carbolic 
acid and pjrrrhol, till the liquid which passes over is no longer coloured 
red, but yellow, by nitric acid; the dark yellow residue distilled with excess 
of soda-ley; the distillate consisting of ammonia, aniline, and leucol, 
distilled wiUi excess of acetic acid, as long as the liquid which passes 
over colours fir-wood yellow, the greater part of the acetate of ammonia 
then remaining in the retort; part qf U>e distillate, consisting of aoetate 



ANILINE. 249 

of aniline and lenool, and a small quantitjof acetate of ammonia^ distilled 
with oxalic acid, whereupon the acetic acid passes over; then, in order 
to saturate the oxalic acid with hases, a second portion, &c <&c. till the 
liquid which passes over colours fir- wood yellow, and therefore contains 
acetate of aniline (which, together with the acetate of leucol, must be 
collected in a separate receiver), a proof that the oxalic acid is saturated. 
The residue in the retort, consisting of oxalate of aniline and leucol, a 
small quantity of oxalate of ammonia, and a brown-red colouring matter, 
is evaporated to dryness, and washed on a filter with 85 percent alcoholj 
as long as anything dissolves, collecting apart the last and slightly 
coloured portion of aJcohol which runs through. That which remains on 
the filter is oxalate of aniline; the slightly coloured alcoholic filtrate 
contains the oxalates of aniline and leucol, which crystallise on evapora- 
tion, and may be so far separated by recrystallisation from hot water (on 
the cooling of which the leucol-salt crystallises first in colourless needles^ 
and then the aniline-salt in laminse), and from alcohol, that the aniline- 
salt, when rubbed between the fingers, no longer smells like phosphorus^ 
and the leucol-salt neither colours fir-wood yellow nor chloride of lime 
violet. By distilling the oxalates with soda-ley, agitating the distillate 
with ether, and evaporating the ethereal extracts, the bases are obtained 
in the free state. (Runge.) 

Properties. Thin colourless oil (Runge), becoming thickish at — 20^ 
but not solidifying (Hofmann) : sp. ffr. 1*028 (Fritzsche); 1*020 at le"* 
(Hofmann); refracts light very strongly (Fritzsche, Hofmann); does not 
at all conauct the current of a 4-celled Bunsen's battery. (Hofmann.) 
Boils steadily at 182'' (Hofmann), at 228° (Fritzsche); at about 200^ 
(Zinin)^ and soon evaporates when exposed to the air (Runge), so that 
an oil-stain produced on paper by aniline, soon disappears. (Hofmann.) 
Vapour-density = 3*219 ^urral, N. Ann. Ckim. Phys. 20, 348.) Smells 
strongly like msh honey (Unverdorben); has a very faint, not unpleasant 
odour, and when inhaled does not act injuriously on the head or lungs 
(Runge); has a strong, unpleasant, aromatic odour (Fritzsche); a peculiar 
odour (Ziuin); a faint, agreeable, vinous odour. (Hofmann.) Its taste is 
somewhat biting (Zinin); aromatic and burning. (Hofmann.) Half a 
gramme of anihne introduced^ together with ll grm. water, into the 
stomach of a rabbit, causes strong clonic cramps, uien laborious breathing, 
loss of strength, dilated pupils, and inflammation of the mucous membrane 
of the mouth; but aniline dropt into the eye does not dilate the pupil. 
(Hofmann.) It does not exert any poisonous action on dogs (W&hler & 
Frerichs, Ann. Pharm. Q5, 343); its aoueous solution kills leeches, and 
cut pieces of plants immersed in it. (Runge.) — Aniline does not bin e 
redcfened litmus (Runge), or redden turmeric (Runge); neither does its 
aqueous solution, which however turns the violet colour of dahlias to 
green. (Hofmann.) It imparts a bright violet-blue colour to chloride of 
fime; and in presence of an acid, a yellow colour to firwood and elder- 
pith. (Runge.) 

Zinin. Zinin. Fritsche. Hofmann. 

from Nitrobenzene, JromAioxi- - ^^ r-A-«-« from Coal- 
benzene, fi-^^^ff^' tar. 

12 C .... 72 .... 77-42 .... 7717 7711 78-21 .... 7731 

N .... 14 .... 15-05 .... 14-84 15-00 1483 

7 H .... 7 .... 7-53 .... 7-61 7-51 7-54 .... 7'72 

gi3NH7,. 93 ".. 100-00 .... 99-62 m 99-62 ........ 100- 58 



250 BENZSIfE: AZO-NUCLEUS C^H*. 

Vol. Density. 

C-Tapour 12 4*9920 

N-gat 1 0-9706 

H.gas 7 0-4851 

AniUne-Tapoor .,.• 2 6*4477 

1 3-2236 

According to Laurent and moat chemists, aniline is C^AdH^ and not Ci'NHMI^ 

j C»H» 
Aooordlng to Hofmann it is phenylamine N{ H , that is, anmonlain which 1 At. H 

I H 
ia repiaoed by f henyU 

Decompofitions. 1. Aniline hums ^hen set on fire, ^itb a laminoas, 
Btronglj fuliginous flame. (Hofmann.) — 2. When exposed to the air, 
it becomes yellow (red, according to Zintn), and afterwards brown, 
forming a resin, which is brown according to Fritzsche, red, and soluble 
with yellow colour in water, according to Unverdorben; tbe change 
takes place the more quickly as the temperature is higher. (Hofmann.) 
Hence in distilling aniline, it is necessary, either to use a brisk fire, or to 
pass a stream of carbonic acid or hydrogen gas through the apparatus. 
(Hofmann.) 

8. Chlorine gas passed through dry aniline, converts it, with great 
rise of temperature and evolution of hydrochloric acid, into a black viscid 
tar, which stops up the gas-delivery tube. If, in order to prevent this 
accident, the chlorine be passed through aniline mixed with water, or dis- 
solved in hydrochloric acid or in alcohol, the liquid, which assumes first a 
blue, then a black colour, deposits a black tar, which on cooling soli- 
difies into a brittle resin; — and this resin distilled with a small quantity of 
water, yields terchloraniline, C"NC1'H*; afterwards liquefies; leaves a 
residue of charcoal; and gives ofi* hydrochloric acid and terchlorocarbolic 
acid in the form of a yellow offensive oil which crystallises on cooling. 
(Hofmann.): 

a^ve + 6C1 - c»Na»H< + shcii 

terchloraniline. 
and : 

C»NBP + 6a + 2H0 - CMCl»H30« + 2C1 + NH*CI. 

terchlorocarbolic acid. 

Terchloraniline appears also to be formed when aniline is distilled with 
hydrochloric acid and peroxide of manganese. (Hofmann.) 

4. Bromine forms with anhydrous aniline, with great evolntion of 
beat, a brown solution, which, if the quantity of bromine is sufficient, 
solidifies to a mixture of finely crystalline terbromaniline and hydro** 
bromic acid. (Fritncbe.) •^- ^romtn^ iiu^rr aikled to aniline dissolved in 
hydrocfalorio acid, forms a considerable quantity of hydrobromic acid, «nd 
a precipitate of terbromaniliiie which quickly becomes crystalline; the 
same substance is deposited, after bmling aailine with excess of hydro- 
bromic acid, in the form of a dark-coloured oil which crystallises on 
cooling. ^Hofman.) — 5. The dark brown solution of iodine in aniline, 
the formation of which is attended with great rise of temperature, soon 
deposits long needles of hydriodate of aniline (Fritzsche, Hofmann), 
while the mother-liquor retains, together with a portion pf this salt and 



AHILINX. 251 

iodine (free, and oapable of extraction by potash), an ioduretted, brown, 
amorphous resin, insoluble in water, aeids and alkalis, but soluble in 
alcohol and ether, and likewise hjdriodate of ipdaniline: formation 
of the last-mentioned compound: 

C»NH7 + 21 - C"NIH«,HI. (Hoftnann.) 

0. With aoueons chloride nf lime, aniline forms an asnre or Tiolet-blue 
solution, which is coloured rose-red by acids and decolorised by a large 

3[uantity of chlorine, in consequence of the formation of an acid [1] which 
brms blue salts with bases, as in this case with lime. Hence coal-tar 
shaken up with dilute chloride of lime, forms a blue watery liquid. 
(Rnnge.) All hypochlorites act like chloride of lime. The blue mixture 
becomes covered in a few minutes with an iridescent film, and gradually 
assumes a dingy red colour (more quickiy with aniline-salts). The alcoholic 
solution of aniline acquires but a faint blue colour when mixed with 
chloride of lime; the ethereal solution, or a solution containing a large 
Quantity of ammonia is not coloured at all. (Hofmann.)— 7. On adding to 
the aqueous solution of an aniline-salt, an equal quantity of alcohol, and 
then hydrochloric acid mixed with chlorate of potash, a considerable 
quantity of indigo-coloured flakes is gradually deposited; and these, when 
collected on a filter and washed with alcohol, become green as they are 
freed from adhering acid, and shrink in drying, into a dark green body 
containing 16 per cent of chlorine. The liquid filtered from the blue 
precipitate contains a brown resin, and when boiled, with addition of 
more hydrochloric acid and chlorate of potash, assumes a light yellow 
colour and yields crystals of chloraniL Bromic acid or a mixture of 
iodate of potash and sulphuric acid, forms with aniline a similar blue 
precipitate. (Fritzsche.) As the proportion of hydrochloric acid and 
chlorate of potash required to form the blue precipitate is not easily 
found, it is better to add to a solution of aniline in hydrochloric acid, a 
few drops of chlorous acid prepared by Millon's process, which imme- 
diately forms a blue magma. The washed precipitate is decomposible by 
ammonia or potash, with formation of sal-ammoniac or chloride of potas- 
sium. By gradually adding chlorate of potash to a boiling mixture of 
strong hydrochloric acid and aniline dissolved in a not too large quantity 
of alcohol, crystals of pure chloranil are obtained, without any blueing of 
the mixture, but with copious evolution of acetic ether and formation 
of sal-ammoniac. When a large quantity of chlorate of potash is thrown 
into a boiling solution of aniline in excess of strong hydrochloric acid, 
a brisk reaction takes place, and chloranil is produced, together with a red 
resin which may be extracted by alcohol, and when distilled, yields, first 
an additional quantity of chloranil, then hydrochloric acid, and after- 
wards a sublimate having the odour and chemical relations of tercbloro- 
carbolic at^id, but probably consisting of quintichlorocarbolio acid. 
(Hofmann.) — 8. Aniline is decomposed by nilric add, and when evapo- 
rated at 100°, leaves a brown-black residue. (Runge.) — It is imme- 
diately reddened by strong nitric acid. (Zinin.) It acquires a transient 
blue and green colour by treatment with strong nitric acid. ^Fritzche.) 
— With a small quantity of fuming nitric acid, it immediately forms a 
deep azure-blue mixture, which when very slightly warmed, turns yellow, 
becomes hot, gives off gas with violence, then assumes a scarlet C'Olour 
continually increasing in brightness, and deposits numerous plates of 
picric acid. (Hofmann.) Aniline, dissolved in moderately strong nitric 
aeidy likewise passes ioto spontaneous ebullitien oa the application of m 



252 BBNZENB: AZO-NUCLEUS C^-NH*. 

gentle heat, giyes off nitrous vapoars, and when that action ceases, is 
found to be converted into picric acid, (Hofmann & Muspratt) : 

OmB7 + 6N0» - C«N«H»0'< + 4HO + 4N0». (Hofmann.) 

9. Aqueous hjdrochlorate of aniline mixed with nUraU of silver (or with 
nitre which has been heated to redness for some time) gives off a larc^e 
quantity of nitrogen gas, and yields carbolic acid in small brown ouj 
drops. (Hunt, Sill. Am. J., 1849; Hofmann, Ann. Fhaim. 75, 356): 

C?«NH' + N0» « C«a»0» + HO + 2N. (Hunt,) 

Hunt produced the same trantfonnation by paaaing nitric oxide gas through a solution 
of aniline in nitric acid, whereas Hofmann, by using comparatively strong add, obtained 
a brown resinous mixture of crystalline nitrocarbolic acid, and an amorphous substance, 
together with a trace of carbolic add, to judge by the odour of castoreum which was 
evoWed; with a weaker acid, no decomposition took place. — 10. OU of Vitriol 

forms with aniline a mixture which turns brown at 100°, and when the 
decomposition is carried further, produces sulphate of ammonia. (Runge.^ 

11. Aniline takes fire, in contact with anhydrous chromic acidj ana 
bums with a bright flame and agreeable odour, leaving sesquioxide of 
chromium. (Hofmann.) — The aqueous solution of aniline and its salts, 
forms with aqueous chromic acid, a precipitate containing chromium, 
which is dark blue, dark green, or black, according to the concentration 
of the solutions (Fritzsche, Hofmann), and varies in composition from 
62-66 p.c. C and 2-12 Cr»0« to 33-93 C and 31-00 Cr^O*. (Fritzsche.) — 
3 2. Aniline and its salts form in solution of permanganate of potash, 
a brown precipitate of hydrated peroxide of manganese. (Fritzsche, 
Hofmann.) — 13. When aqueous sulphate of aniline is boiled with 
peroxide of lead, carbolic acid is evolved, and a blue liquid produced, 
which smells of formic acid, afterwards becomes colourless, and gives 
off ammonia when treated with potash. (Hofmann.) — 14. With ferric 
sulphate, sulphate of aniline forms a dark red mixture from which 
ferrous sulphate crystallises. (Hofmann.) — 15. Aniline heated with 
solution of silver, forms a black brown precipitate, and with soltUion of 
gold, a purple floccnlent precipitate. (Ruuffe.) 

16. With terchloride of phosphorus, aniline forms a crystalline sub- 
stance. (Hofmann.) — 17. In phosgene gcu it becomes heated and soli- 
difies into a crystalline mixture of carbanilide and hydrochlorate of 
aniline : 

4C"NH7 + 2CaO - C»N«H»0* + 2(C'^H',Ha). (Hoftnann.) 

18. Aniline mixes in all proportions with bistdphide qf carbon, the 
mixture giving off sulphuretted hydrogen, after standing for several 
hours, and solidifying after some weeks (more quickly in a warm place 
or on addition of alcohol), forming scaly sulphocarbanilide : 

2C"NH' + 2CS» = C?«N«HMS« + 2HS (Hofmann). 

20. Aniline mixed with iodide qf methyl, boils briskly and forma 
crystals of hydriodate of methylaniline: 

C«NH7 + C«H»I = (?<NH»,HI. 

Similarly with bromide of methyl, it quickly solidifies into a mass of 
hydrobromate of methylaniline. (Hofmann. )h— 21. Cyanogen gas passed 
through pure aniline is quickly absorbed, with evolution of heat, and a 
reddening of the Uquid amounting to opacity; an odour of hydrocyaaio 



AKILINB. 253 

acid is at tlie same time prodnced, whicb^ when the passage of the gas is 
oontinaed, changes into that of cyanogen, but after the vessel has been 
closed for 12 hours, again passes into that of hydrocyanic acid; the 
liquid deposits crystalline but brown cyaniline^ and, if sufficient cyanogen 
is present, finally solidifies into a dark crystalline mass. When cyanogen 
is passed through an alcoholic solution of aniline, only till the liquid smells 
strongly of it, crystals of nearly pure cyaniline are deposited; but when the 
passage of the gas is further continued, other products mix with the 
oyaniline, just as when the sas is passed through pure aniline. (Hofmann.) 
— 22. Anhydrous aniline SLOSorbs the yapour of cyanic acid evolved from 
heated cyanuric acid, becoming hot, and solidifying as it cools, in the 
form of crystalliQe aniline-urea, C"N'HH}*, mixed with a quantity of 
carbanilidoy CN'U^'O^, greater, as the liquid has become more strongly 
heated : 

C^W + C«NH02 = C"N»H802L 

The same aniline-urea is precipitated in the czystalline form on adding 
emanate of potash to aqueous sulphate of aniline. (Hofmann, Ann, 
Pkarm. 53, 57; 57, B65.) Chancel (Compt. chim. 1849) obtained by the 
latter process nothing but cyanate of aniline, which gave off all 
the aniline on being boiled with potash. — 23. Gaseoita cJUaride of 
cyanogen dried by chloride of calcium is absorbed abundantly and with 
great evolution of heat, by dry aniline, which then becomes darker in 
colour, and thickens into a crystalline magma, so that it requires to be 
heated in order to saturate it with the gas ; the resinous mass which 
then solidifies on cooling consists of hydrochlorate of melaniline* 
C»N»H« HCl : 

2CMNH7 + C*NC1 = C»N»HMCL 

This product is however mixed with aniline-urea, the quantity of which is 
larger, in proportion as the exclusion of water has been less carefully 
attended to; aqueous chloride of cyanogen produces scarcely anything 
but this compound, mixed with hydrochlorate of aniline : 

2C^W + 2H0 + CWa » C"N«H»08 + CMNH^HQ. 

(Hofmann, Ann. Pharm, 67, 130; 70, 129.) — [According to Gahours 
and Cloez (fiompU rend, 38, 354), dry chloride of cyanogen passed 
through an ethereal solution of aniline cooled with ice, forms nothing 
but cyaniline C^NCyH", and hydrochlorate of aniline : 

2CJ«NH7 + CyCl = Ci«NH7,HCl + C»NCyH» ; 

and by heating the mixture of cyaniline and hydrochlorate of aniline in 
alcoholic solution, a crystalline body is formed from which ammonia 
separates melaniline.] — 24. Bromide of cyanogen acts upon aniline like 
volatile chloride of cyanogen, converting it into hydrobromate of mela- 
niline, and [in presence of water f] a small cruantity of carbanilide. 
(Hofmann.) — 25. Iodide of cyanogen forms with anilme : iodaniline, a 
brown product containing iodine, and hydrocyanic acid. (Hofmann.)-^ 
26. When Hydroperevlphocyanic acid is heated with anhydrous aniline, 
the mixture melts and solidifies on cooling, into a mass which dissolves 
in boiling alcohol and ether, and when boiled with water containing a 
little potash, leaves a residue of sulphur, and 3rields a filtrate from which 
hydrochloric acid precipitates, together with sulphur, crystalline scales 



264 BENZENE: AZO-NUCLEUS d^NH^ 

which dissolve in boiling alcohol and ether. (Laurent & Gerhardt^ jAT. Ann* 
Odm, Fhy$. 24, 1 98.) 

27. The anhydroos mixture of bromide of ethyl and aniline does not 
decompose in the cold, but when heated in an apparatus which allows 
the TolatiliBing bromide of ethyl to condense and flow back again^ passes 
into spontaneoas ebullition, turns brown, and then solidifies in a crystal- 
line mass on cooling. If the aniline is in excess, the crystals consist of 
hydrobromate of aniline, while the mother-liquor contains ethylaniline 
together with free aniline : 

2C»NHy + C<H»Br - CnNH7,HBr + C»«NH»». 

With an excess of bromide of ethvl, the crystals consist of hydrobromate 
of ethylaniline, and the mother^liquor contains the same mt together 
with bromide of ethyl : 

CmW + C*H»Br =» C»«NH»,HBr. 

With a medium proportion, the two kinds of crystals are produced 
together. (Hofmann.) — ^ 28. The solution of aniline in cyanuric ether 
(ix, 459), the formation of which is attended with considerable evolution 
of heat, solidifies, on cooling, in the form of crystalline ethykniline-urea 
Qi8j^H^K)*. (Wurtz, Compt. rend. 32, 417.) — The mixture of aniline 
and mustard-inl deposits, after four months, four-sided tables, perhaps of 
C"N*H"S*, homologous with thiosinnamine. (Hofmann.) — ^. On mixing 
1 At. mustard-oil and 1 At. aniline in alcoholic solution (I pt. aniline to 
4 pts. of 90 per cent, alcohol), the mixture soon becomes neated, loses 
nearly all the odour of mustard-oil, and on cooling yields crystals con- 
sisting of a compound of the two bodies : 

C»NH' + C«NH»S* « C«WH»«8«. 

(Zinin, Ann, Pharm, 84, 346.) %. — 29. A cold mixture of aniline and 
excess of bromide of amyl deposits after some days, crystals of hydro- 
bromate of aniline, while the mother-liquor contains amyianiline together 
with bromide of amyl; but when the bromide of amyl is in very large 
excess, and the mixture is heated in the water-bath, hydrobromate of 
amylaniliue separates from the bromide of amyl in the crystalline form. 
(Hofmann.) 

lylaniline. 



and: 

C»NH' + CWH»Br = C«NH»7,HBr. 

Aniline is not altered by being heated with carbolic acid to 250^ for 
several days in a sealed tube. (Hofmann.) 

30. Aniline, in combination with organic acids, is converted, by 
abstraction of 2 or 4 At. water, into conjugated compounds, some of 
which are alao produced by aniline and certain chlorine-compounds 
belonging to the aldides, which form acids with water. The following 
classes are to be distinguished : 

1. Anilie acids, corresponding to the amidogen-acids, compounds of 
1 At. aniline and 1 At. of a bibasic acid minus 2 At. water : e.g, 

C»NH"0« « C^2jcH7 + C»H«08 - 2H0. 
sacdiwnilic add. 



ANILINB. 255 

TLej du»olve bat sparingly in water, more easily, however, tlian the 
following compounds : 

2. Anilides, compounds analogous to the amides, either of I At 
aniline with 1 At. of a monobasic acid minus 2 At. water, or of 2 At. 
aniline with 1 At of a bibasic acid minus 4 At water, the latter to be 
fnrther distingnished as Dianilides : t, g. 

«C»NH7 + C*HH)8 - 4H0 «» C«N«HM0*5 

ozamlide* 

or of 1 At. aniline ^th 1 At. of a chlorine-compound minus 1 At 
hydrochloric acid; e.g, 

CMNH» + CMCIHW - HCl - C»NH»0» 



chlorobenzoyL benxuiUide. 

Many anilides rolatilise when strongly heated. With melting hydrate of 
potash, they give off aniline, but not with boiling potash-ley. They are 
rasoluble or sparingly soluble in water, but dissolve much more readily in 
alcohol. 

S. AnUs, compounds analogous to the imides (vii, 200), of 1 At. 
aniline and 1 At. of a bibasic acid minus 4 At water : e,g, 

C»SNH' + C»H60» - 4H0 = C^NH»0«. 

succinanU. 

They mostly rolatilise when strongly heated. When boiled with aqueous 
ammonia, they take up 2 At. water, and are converted into a compound 
of ammonia with the corresponding anilie acid : 

C»NH»0< + 2H0 - C»NH"0». 



\«i 



Euccinanilic acid. 

With potash they behave like the anilides. They dissolve in alcohol 
much more readily than in water. (Laurent &, Gerhardt, N. Ann, Chim. 
Fhys, 24, 163; comp, Hofmann. Ann. Phai'm, 73, 33.) 

Combinations. When pure aniline obtained from the oxalate is shaken 
up with vHUer, Hydrated Aniline is formed (probably containing only 1 At. 
water) and an aqueous solution containing very little aniline. (Hofmann.) 
Hydrated aniline when distilled, yields at first a distillate consisting 
chiefly of water, so that the last two-thirds are anhydrous. (Fritzsche.) — 
Aniline which has not been freed from the offensive-smelling substance (odorine) by combi- 
nation with oxalic acid (p. 248), dissolves much more abundantly and forms a lower layer 
consisting of a much more saturated solution of aniline in water, and an upper layer of 
hydrated aniline containing a much larger proportion of water, viz. 30 p. c. (more than 4 At. 
water), and becomes turbid even at the heat of the hands. — Pure aniline dissolves 

in water more abandantly the higher the temperature, so that a solution 
saturated at a boiling heat becomes milk-white on cooling. From a 
solution prepared in the cold^ the aniline is separated by caustic potash 
or soda or their carbonates, also by common salt and sulphate oi mag- 
nesia; and ether dissolves it out n*om the water. But the cold-saturated 
aqueous solution of aniline still containing odorine, becomes turbid even at the heat of 
the hand, and when boiled, yields a large qoantity of hydrated aniline which rises to 
the surface ; it is also rendered turbid by 4 drops of sulphuric or oxalic acid, and 



256 BBNZENE : AZO-NUCLEUS CWNH«. 

becomes clear only on the addition of a large quantity, whereas the solution of pure 
aniline remains clear when thus treated. (Hofmann.) — Aniline dissolTes readily in 
water (Runge); sparingly (Fritzcbe); not at all. (Zinin.) 

Aniline dissolves phosphorus with tolerable facility (Hofmann), 
sulphur yery abundantly with the aid of heat, and deposits it in the 
crystalline form on cooling (Fritzschej Hofmann); it mixes in all propor- 
tions with sulphide of carbon, (Hofmann.) 

Aniline combines with acias, the combination being attended with 
rise of temperntare (Hofmann) and neutralisation of the acid (Runge), 
and forms the AnUine-saUs, It precipitates the salts of alumina, zinc- 
oxide, ferrous oxide and ferric oxide, but not those of magnesia; chromic 
oxide, manganous oxide, cobalt-oxide or nickel-oxide; neither does it 
form any precipitate with mercnrous nitrate or nitrate of silver. (Hof- 
mann.^ Its compounds with inorganic oxygen-acids contain water as an 
essential constituent (Zinin, Fritzsche, Hofmann.) Most aniline-eodts 
crystallise readily. (Unyerdorben, Zinin.) — Sometimes the offensive-smelling 
substance (the odorine) in aniline which has not heen separated from the oxalate, inter- 
feres with the crystallisation. (Hofmann.) — The salts are mostly colourless and 
inodorous. (Hofmann.) When exposed to the air, they assume a rose 
colour, especially when moist. (Hofmann.) Fixed alkalis separate the 

aniline from them in oily drops; so does ammonia at ordinary tempera- 
tures, whereas at higher temperatures the ammonia is expelled by the 
aniline. (Hofmann.) From the dried salts, potassium-amalgam elimmates 
hydrogen and aniline. The aniline-salts, especially the hydrochlorate and 
nitrate, give, with chloride of lime containing excess of lime, an azure- 
blue solution (p. 251); this coloration is least intense with the acetate. 
To firwood or elder-pith, in consequence of the presence of a substance 
which may be extracted by water or alcohol (but not to paper, linen, 
cotton, silK, or wool), they impart a deep yellow colour, which is not 
destroyed by chlorine, and is still perceptible in a solution containing 

^°^7 8 6 6^656 ^^ aniline. (Runge.) — The salts of naphthalidam produce this 
colour with greater intensity, those of leucol produce it after a while, whereas those of 
sinnamine, conine and chinoline, yield only a pale yellow colour. (Hofmann.) 
Aniline does not combine with carbonic acid. (Hofmann.) 

Ordinary/ Phosphate of Aniline.-— a. Bibasic — Concentrated phos- 
phoric acid supersaturated with aniline, solidifies immediately in a white 
crystalline mass, which, after being pressed, dissolved in a large quantity 
of boiling alcohol, strained through a hot filter, and cooled, yields flesh- 
coloured, nacreous, inodorous laminte, which slightly redden litmus; they 
nmst be pressed between paper and dried on a warm tile. At 100^ they 
turn red and give off aniline; melt at a stronger beat, and finally leave 
metaphosphoric acid (coloured, according to Gerhardt, by the carbonisation 
of a small quantity of aniline) while the aniline volatilises. They dis- 
solve readily in water and ether, sparingly in cold alcohol, but so abun- 
dantly in hot alcohol, that the liquid solidifies on cooling. (£. C. 
Nicholson, Ann, Fharm. 59, 213.) 



OA P 


Cryitcdt. 
144-0 


.... 50-63 .. 
.... 9-85 
.... 6-97 .. 
.... 8 44 
.... 26-11 .. 


Kicholson. 
50-16 


2N 


280 




17 H 


17-0 


6-10 


3 


24-0 




P0» 


71-4 


24-86 



2(C"NH7,HO),Aq,cPO* 28i-4 .... 100-00 



ANILINE. 257 

h. Monobasic. The aqueous solution of the salt a mixed with phos« 
phorio acid, till it no longer precipitates chloride of barium, yields, in 
a few hours, after eyaporation oirer the water-bath, white silky needles, 
which must be cooled with ether and dried on a warm tile; they turn red 
in the air, and dissolve readily in water, alcohol and ether; in water, 
however, the salt a is formed at the same time. (Nicholson.) 

Cfrysiali. 

12 C 

N « 

10 H 

3 O 

PO» 







Nicho]Bon. 


720 


.... 37-62 .. 


37-86 


140 


.... 7-32 




100 


.... O'Zfi •• 


•....4 u'44 


240 


.... 12-54 




71-4 


.... 37-30 .. 


37-12 



C"NH7,HO,2Aq,cPO».. 191-4 .... 10000 

Pyrophogphate of Aniline, — Concentrated pyrophosphorio acid ob- 
tained by decomposing pyrophosphate of lead with sulphuretted hydrogen, 
forms with excess of aniline, a gelatinous hardening precipitate which is 
a mixture of hihasic and monobasic salt The former cannot be prepared 
In the pure state; but the monobasic salt is obtained, by heating the 
mixture till solution takes place, supersaturating with acid, and evapora- 
ting over the water-bath, in the form of a needle-shaped mass which 
solidifies on cooling; it must be pressed between paper, washed with 
ether, and dried in vacuo. The silky needles resemble sulphate of quinine, 
are strongly acid, turn red on exposure to the air, both in the solid state 
and in solution, and are soluble in water, but quite insoluble in alcohol 
And ethez. (Nicholson.) 

Crystals dried in vacuo, Nicholson. 

12 C 72-0 .... 39-47 3942 

N 14-0 .... 7-68 

9H 90 .... 4-93 6-56 

2 160 .... 8-77 

P0» 71-4 .... 39-15 38-85 

C«NH7,HO,6PO» + Aq .... 182-4 .... 10000 

Metaphosphate of Aniline. — The concentrated solution of glacial 
phosphoric acid added in large excess to aniline or to its solution in 
alcohol or ether, throws down a white jelly, which must be washed on 
the filter with ether, till the odour of anihne disappears, and dried in 
yacuo over oil of vitriol* White amorphous mass, which reddens litmus, 
becomes glutinous and rose-coloured on exposure to the air, and dissolves 
in water, but is quite insoluble in alcohol and ether. The aqueous solu- 
tion is altered by boiling, in consequence of the formation of ordinary 
phosphoric acid; it dissolves metaphosphate of silver, but afterwards turns 
red on boiling, the silver-salt being partly reduced. (Nicholson.) 

Dried in vacuo, Nicholson. 

12 C 72-0 .... 41'52 41-33 

N 140 .... 8-08 

8 H 8-0 .... 4-61 4-55 

O 80 .... 4-61 

aP(y 71-4 .... 41-18 41-11 

C"NH7,HO,aPO* 173-4 .... 100-00 

VOL. XI. Jl 



258 BENZENE: AZO-NtJCLEUS C»'NH». 

Sulphite of Aniline, -^ When BulphurooB aoid gas is absorbed by 
anilinei crystals are formed. (Hofmann.) 

Sulphate of Aniline, — Dilate sulphorio acid remores the odonr of 
aniline, and yields, on eraporation, oTen when the aoid is in exoess, 
crystals of the nentml salt, which may be washed with oold absolnte 
alcohol, crystallise in large laminfls from boiling absolute alcohol, and 
taste of aniline. (Unverdorben.) — The ethereal solution of the oily 
mixture of aniline, leucol, and a small quantity of nentral oil (p. 248), soli- 
difies when mixed with a small quantity of oil of vitriol, forming a white 
cryfitalline magma, which may he freed from leucol by washing with cold 
absolute alcohol, then dissolved in boiling alcohol, separated by filtration 
from a small quantity of sulphate of ammonia, and obtained in crystal- 
line crusts by spontaneous evaporation. (Hofmann.) — The concentrated 
alcoholic solution of aniline solidifies with oil of vitriol, into a white 
mass, which crystallises from boiling alcohol^ in white silvery lamin» 
having a sharp, slightly acid and bitter taste. (Zinin.) — - Dilute sulphuric 
aoid supersaturated with aniline yields, on evaporation, a white crrstalline 
mass which is permanent in the air and reddens litmus. (Runge.; ^-* The 
cnrstalSi when exposed to the air, acquire the odour of aniline, a formation 
of fusoine taking place at the same time (Unverdorben); ther also turn 
red on exposure to the air, especially if moist. (Zinin.) — The orjrstala 
may be dried at 100° without decomposition^ beyond the production of a 
slight brown colour. (Hofmann.) When heated, they give off, first a 
little water, then aniline, and leave an acid salt, which| when further 
heated, leaves a residue of charcoal, and yields a mixed crystalline subli- 
mate of sulphite of aniline, ammonia, and odorine. (Unverdorben.) At 
.a stronger heat, they quickly become carbonised and give off water^ 
sulphurous acid, and a small quantity of ammonia. (Runge.) They first 

five off aniline, then sulphuric aoid, and leave a tumefied, slowly com- 
ustible charcoal. (Hofmann.) When set on fire on platinum foil, they 
bum with a reddish sooty fiame, and leave a large quantity of charcoal. 
(Zinin.) The salt dissolves very readily in water and alcohol (Zinin.) 
The aqueous solution saturated at a boiling heat solidifies on cooling; 
dilute aloohol dissolves a large, cold absolute alcohol a small quantity, 
hot absolute alcohol a large quantity, and ether none. (Unverdorben, 
Hofmann.) 

At 100*. 2inln. Hofbiaitn. 

12 C 72 .... 5071 60-21 

N 14 .... 9-86 

8 H 8 .... ft'68 , 6-90 

8 .... 6-63 

SO« 40 .... 2817 28-99 .♦., 28*67 

OWNH'jHCSO*. 142 .... 100-00 

ffydriodaie of Aniline, — Needles, which dissolve very readily in 
water and aleohoi, less readily in ether. (Hofmann.) 

NeedUi, Hoftnann. 

C»«NH'' 93 .... 42-27 

HI 127 .... 67-73 67-63 

C^^NH^HI 220 .... 100-00 



ANILINB. 259 

HydrchrcmaU qf ^m/tn«. — Sablimes withoat deoomposition^ eren 
when rapidly heated. (Hofmann.) 

Hydrochlorate of Aniline, — Hjdrocbloric add held over aniline> forms fiimei, 
acoordinK to Hofmanni bat according to Range it does not — Hydrochloric acid 

supersaturated with aniliue yields by evaporation, crystals which sublime 
and melt at the same time, redden litmus, dissolve very readily in water, 
alcohol and ether, and when mixed with nitre, blacken at a gentle heat, 
with an odour like that which is emitted during the sublimation of indigo. 
(Runge.^ The salt, which dissolves very readily in water and alcohol, 
crystallises from aJcohol in white lammsa, which sublime readily and 
without decomposition, in the form of a loosely coherent powder, con- 
sisting of delicate needles, and having a saline bitter taste. (Zinin.) 
With strong hydrochloric acid, pure aniline solidifies immediately into a 
crystalline pulp. The salt crystallises from water or alcohol in slender 
needles which have a pungent taste, and sublime without decomposition* 
Aniline not purified by combination with oxalic acid, and still retaining 
an unpleasant odour, does not yield crystals with strong hydrochloric 
acid, but solidifies after a while into a thick uncrystallisable syrup; and 
its solution in ether immediately deposits a similar syrup when nydro- 
chloric acid gas is passed through it. (Hofmann.) 

Crytak. Fritasdie. Zioin. 

12 C 720 .... 55-64 .... 55-08 

N 14-0 .... 10-82 

8 H 80 .... 618 6*05 .... 6-42 

CI 35-4 .... 27-36 27-18 .... 26-58 

CMNH^HC1.... 129*4 .... 100-00 

Nitrate of AnUine.'^l^MriQ acid supersaturated with aniline yields 
on evaporation, colourless, non-deliquescent needles, which redden litmus, 
blacken at 100^, only in presence of free acid, or after being moistened 
with protochloride of copper; and when heated alone above 100°, are 
quickly converted, with slight detonation, into a black mass. (Runge.V-* 
A mixture of aniline and dilute nitric acid yields, after a while, bundles 
of needles, which must be purified by pressure between paper. <rbe red 
mother-liqnor yields blue efflorescences. With moderately strong acid, aniline solidifies 
into a rose-coloored crystalline mass; bnt with stronger acid, it is decomposed, and 
saddenly assames a darker colour. The crystals melt when cautiously heated, 
and are converted, with slight decomposition, into a colourless vapour, 
which condenses in delicate crystalline flowers. But when rapidly heated 
on platinum foil, they give off aniline and become carbonised. (Hofmann.) 

Aniline produces, both with tirchloride qf antimony and with bichloride qf iim 
copious wliite curdy precipitates which crystallise from hot hydrochlorio add* 
(Hofmann.) 

FltLoride ofSUieium with Aniline. — 93 pts. of aniline absorb 63.3 
pts. of gaseous fluoride of silioium, and form a pale yellow mass, which 
when washed with ether, well boiled with alcohol, pressed, dried and 
sublimed, is converted into a very light crust. This product contains 
59*52 p. c. C, 4 '40 H, and when ignited with excess of oxide of lead, 
which expels the aniline, leaves 42 2 p. c. F and SiO*. Water separates 
from it gelatinous silica. It dissolves sparingly in boiling alcohol, and 
crystallises from it in laminsd having a very strong lustre. (Laurent & 
Delbos, N. Ann. Ch/im. Phy$. 22, 101, abstr. If. J. Fharm. 10, 309.) 



260 BENZENE: AZO-NUCLEUS C^^NHV 

Sulphate of Copper with Aniline. —Sulphate qf CupraniHum. C»NH7Ca,SO*. 
[aniliura « C^NH^].— First observed by Hofmann.— Obtained by precipitating 
a dilute solution of sulphate of copper with aniline suspended in water 
and mixed with a sufficient quantity of alcohol to render the liquid clear. 
Pistachio-green crystalline scales, which must be waahed with water and 
dried, first by exposure to the air, then at 100°. When thus prepared, they 
contain 185 p. c. copper, and therefore consist of C"Nir,CuO,SO*. When 
heated, they give off half their aniline, and leaye a black mixture of cnprio 
oxide and cuprio anilosulphate, which last may be extracted by water, 
and recognised by the rod colour which it produces with chromic acid ; 

2CBNH'CuSO* - CWNH' + C»NH«CuSK)« + CuO + HO. 

When the scales are boiled with water, aniline volatilises and sulphate of 
aniline dissolves, while bibasic cupric sulphate remains. (Uerhardt) : 

2C»2NH7CttSO* + HO - a^W + C^NH'SO* + 2CaO,SO». 

With protochloride of copper, aniline forms a precipitate of ^milar 
character, but which very easily turns black. (Hofmann.) 

Chloride of Mercury with Aniline. — lh^ crystalline precipitate which 
aniline forms with corrosive sublimate was first observed by Zinin. 

a. With 1 At Chloride of Mercury. — Chloride of Mereuranilium 
C«NH7Hg,Cl. Alcoholic aniline in excess is precipitated by alcoholic 
corrosive sublimate. Nacreous precipitate, which must be collected on a 
filter and washed with a small quantity of alcohol. It gives off a small 
quantity of aniline even at 60% and turns yellowish. (Gerhardt.) 

GerbardU 

12 C 72-0 .... 31-52 31-2 

N 14-0 .... 6-13 

7H 7-0 .... 3-07 

HgCI 135-4 .... 59*28 



C«NH7HgCI 228-4 .... 100-00 



(. With S At. Chloride of Mercury. — Rises to the surface as a pastr 
mass when aniline is mixed with [excess of )J aqueous corrosive subli- 
mate; on mixing the alcoholic solutions, it is precipitated in the form of 
a soft white powder, which soon becomes crystalline. It must be washed 
with water. When boiled with water, it turns lemon-yellow, with 
evolution of a small quantity of aniline, and partial solution of the salt 
which crystallises out without alteration on cooling. In a small quantity 
of hot hydrochloric acid, it dissolves partially and melts into a heavy red 
oil; in a larger quantity it dissolves completely, and yields white ciystals 
on cooling. In cold wat-er it dissolves very sparingly; slightly also in 
boiling alcohol, from which it crystallises on cooling. (Hofmann.) * Of the 
same composition also are probably the needles which Gerhardt obtained 
by further addition of corrosive sublimate to the alcoholic liquid filtered 
from the salt a; this liquid when boiled with alcohol, yielded an orange- 

Jrellow residue, and a dark yellow filtrate from which a mixture of colour* 
ess and orange-yellow crystals was deposited on cooling. 



ANILINB« 361 

Hofmann* 

12 C ^ 720 .... 14-43 •„...« 14*20 

N 14*0 .... 2-81 

7 H 70 .... 1-40 

3 Hg 300-0 .... 6009 ........ 60-63 

3 CI 106-2 .... 21*27 20*36 

C"NH',3HgCl .... 499-2 .... 100-00 
May be regarded as Ci^H7HgCl,2HgCl. 

With terchloride of gold, aniline forniB a red-brown, and hjdrochloraie 
of aniline a yellow precipitate, the colour of which quickly changes to 
dingy red-brown. (Hofmann.) 

ChloroplcUinate of Aniline. — Aniline dissolred in a large quantity of 
hydrochloric acid quickly solidifies with aqueous bichloride of platinum, 
into an orange-yellow crystalline pulp : if the solution of hydrochlorate 
of aniline was preyiously mixed with an equal volume of alcohol, slender 
needles are more slowly formed on addition of the platinum-solution. 
If the aniline in the mixture predominates over the hydrochloric acid, it 
turns brown, in consequence of the formation of decomposition-products. 
The crystals are washed with a cold mixture of ether and alcohol, and 
dried. They dissolve sparingly in a mixture of ether and alcohol, but not 
in pure ether. (Hofmann.) The brownish-yellow precipitate sparingly 
soluble in water and alcohol, which Zinin obtained by adding pure aniline 
to solution of platinum appears from analysis, after careful washing with 
ether and alcohol, and drying at 100°, to be identical with this compound. 

Zinin, 



12 C 


At 100^ 

72-0 


.... 24*07 .. 
.... 4*68 
.... 2*70 .. 
.... 33*06 ... 
.... «Sd-4«f ... 


Hofmann. 
2415 


N 

8 H 


140 

80 


2-67 


Pt 

3 CI 


990 

106-2 


32-89 

34-82 



32*43 



C»NH»Cl,PtCP .... 299*2 .... 100-00 100-00 

With chloride of palladium, aniline forms a precipitate of a fine 
orange-yellow colour. (Hofmann.) 

Sulphocyanaie of Aniline, — Aqueous hydrosulphocyanic acid saturated 
with aniline deposits on evaporation, red oily drops which gradually 
flolidifv in the crystalline form. The crystalline mass melts when gently 
heated; then gives off sulphuretted hydrogen and sulphide of ammonium, 
-with violent ebullition; and when more strongly heated, yields an oily 
distillate of sulphide of carbon and sulphide of ammonium together with 
sulphocarbanilide, and leaves a pale resinous residue : 

2(C>«Nir,C»NHS«) «= C»N«H«S2 + c^NSH^S'. 

salphocarbanilide. sulphocyanide 

of amrooniam. 

But the latter is further resolved at the given temperature into salphide 



262 BENZENE: AZO-NUCLEUS C»NU*. 

of carbon, stilpliide of aniTDonium, and a residae of mellone, to whieh 
however an aniline-compound adheres. (Hofmann.) : 

2Ci^H7 + CNHS* » C»N*H»SS + NH*. (Unrent & Gerhaidt.) 

Acetate of Aniline. — Does not oryBtallise; maj be distilled over with 
water. (Runge.) 

Oxalate of Aniline. -^^ Bibasic. — The alcoholic solutions of aniline 
and oxalic acid, deposit when mized^ a white powder, which, after 
washing with alcohol, crystallises from hot water in long needlea 
(Fritzsche.) The crystalline pulp obtained on mixing aniline with alco- 
holic oxalic acid, cirstallises on cooling from solution in the smallest 
possible quantity of boiling water, in oblique rhombic prisms united in 
stellate groups, whose solution reddens litmus. ^Hofmann.) From water 
the salt crystallises in broad laminae; from alconol, in needles united in 
stellate groups. The precipitate formed in aniline by excess of oxalic 
acid, after being washed with water and sereral times reorystallised, is 
likewise a needle-shaped bibasic salt containing 61 *01 p. c. C. (Hofmann.) 
At 100*', the crystals give off aniline slowly but continuously, and assume 
a yellow colour. The aqueous solution quickly becomes coloured on 
exposure to the air, and deposits a brown-red powder. (Hofmann.) The 
crystals when heated, give off aniline and water, and then sublime in 
the form of an acid euJt. They decompose at a temperature somewhat 
abore 100^, fusing, boiling, and giving off aniline and carbonic acid, 
with which, between 160° and 180 , there is likewise associated carbonic 
oxide (and, according to Hofmann, a trace of anilocyanic acid). At 
this temperature, there remains a clear red liquid, which, on cooling, soli- 
difies into a buttery mixture of oxanilide and formanilide : 

2C»NH',C<EP0» « C«N«HMO< + 4H0; 

oxanilide. 
•ad: 

2CMNH7,C<H«0» - C"NH70« + CMNH' + 2C0» + 2H0. (Geihwdt) 

formanilide. 



% Perfectly pure oxalate of aniline may be heated in the oil-bath 
to temperatures between 160° and ISO'', without fusing, and without 
production of formanilide, the residue, which is perfectly white and crys- 
talline consisting wholly of oxanilide. But oxalate of aniline in a less 
pure state, melts and yields formanilide as well as oxanilide (Piria, II 
nuovo Cimento, 2, 305; InitU. 1856, 224). IT. — The crystals are less 
easily soluble in water, alcohol and ether than other aniline-salts 
(Runge); they dissolve readily in water, sparingly in absolute alcohol, 
not at all in ether. (Hofmann.) 

Cryttals. Fritncfae. Hofmann. 

28 C 168 .... 60-87 61*67 .... 6125 

2N 28 .... 1015 10-21 

16 H 16 .... 5-79 5-77 .... 6-05 

8 64 .... 23-19 22-35 

■ 2C^H7,C*HS0« 276 .... 10000 10000 



PICOLINB. 263 

v. MeUitaU &f Aniline. O^W^VWV. ~ When aqueous aniline is 
flfaaken up with a solution ol mellitio aoid, a turbid liquid is obtained 
which gradnaily deposits scaly laminsB resembling those of bensoio scid. 
The crystals dissolye readily in water; alcohol also dissolves them when 
hot, but the solution does not yield crystals. They do not undergo any 
alteration at 100^ but at 105 , they turn yellow and give off aniline. 
(Karmrodt, Ann, Fharm, %l, 17S.) f • 

Butyraie of Aniline. ^^OWj liquid, easy to distill sparingly soluble in 
water. (Unrerdorben.) 

8uccinaie of AnUme, — Thin, oblique teetaogular prisms, of a pale 
rose oolour. (Gerhardt) 

TariraU ofAniUne. -*- The aqueous acid solidifies with aniline. The 
salt crystallises from hot water in needles. (Hofmann.) 

f Sulphoben9olal0 ^AniUn$ C'H'CC^NH^jiS'O'. — 8u(pkopkif^iai$ qf 
Aniline, -^ Obtained by dropping aniline into a hot solution of sulphoben- 
solio acid. (p. 155.) Ci^stsllises in long silky needles arranged in 
stellate groups, and genemlly exhibiting a reddish tint They melt at 
20 1^ and the fused salt solidifies in a stellate orystalUne mass; it 
sublimes below the melting point in colourless crystals. Dissolves readily 
in water and alcohol, sparingly in ether* (Gerioke, Ann, fharm^ 
0, 817.) H 

FicrcUe qf Aniline, — The lemon^yellow precipitate which an excess 
of alcoholic picric acid forms with aniline, dissolves in boiling alcohol, 
and crystallises on cooling. (Hofmanu,) 

Aniline mixes in all proportions with toood-epirU, alcohol, ether, 
Mehyde and acetone* (Hofmann.) Stber abstracts it from its aqueous 
solution. (Runge.) 

Aniline mixes in all proportions with oils both fixed and volatile; it 
dissolves common eamphor and oolopbonium, but not copal or caootcboua 
It coagulates white of egg, (Hofinann.) 



FicoUne, 

C»NH^ = C"AdH»,H*. » 

Unvbrdorbbk. Pogg. 8, 259 and 480; 11, 59. 

Akderson. N. Bd. Phil. J. 41, 146 and 291; also Ann, Pharm. 60^ 86; 

also J, pr; Chem. 40; 481.— PAi^. Mag. J. [3], 33, 185; also J. pr. 

Chem. 45, 166. -~ Further t £d. PkU. Tram. 21, Ft. X. 219; Phil. 

Mag. J. [4], 9, 214 ; Ann. Pharm. 94, 858. 

Odmrine. — The base OdoHne, diecoTered In 1826 by Unverdorben in bone-oil, — 
together with three other leae voUtile aUceloidt, reterred for more preciee ioTestigation, 
and named from Oleum animale, Animitu, Olamne, and .^mme/tfif,— waa obtained in 
greater pnrity and mote exaotlf inf estigated oy Anderaon in 1846, as Pieolime. 

FormaHon. I. In the dry distillation of bones, and in smaller quan* 
tity, in that of coal [also, of certain varieties of bituminous shale 



264 BENZENE : AZO-NUCLEUS C»NH<. 

(C. 6. Williams, Chem, Soc. Qu, J, 7, 97)]. The bones, from wbich the 
greater part of the fat is generally removed by boiling with water, yield by 
dry distillation, an oil, which when separated from the watery distillate 
and rectified, is of a greenish black-brown colour; exhibits a brown 
colour by transmitted light only in thin layers; has a density of 0*970; 
an ofTensive ammoniacal odour; diffuses vapours which impart a dark purple 
colour to deal shavings moistened with hydrochloric acid (the pyrrhol 
described by Runge, GUb, 31, 67); yields to alkalis a large quantity of 
hydrochloric acid and an acid oil [carbolic acid ?], while to acids, it yields 
ammonia, alkaloids, and a neutral oil which separates in orange-yellow 
resinous flakes, slowly in the cold, immediately when heated, the quantity 
of (his oil being greater, the more concentrated the acid. In the rectifi- 
cation of the oil, there passes over, first an ammoniacal watery liquid 
containing volatile alkaloid in solution, then a transparent, pale yellow 
very volatile oil, containing petinine, odorine, and aniline, and displacing 
the watery liquid more and more as the distillation proceeds : — then 
when -I of the whole have passed over, and the heat has increased, an oil 
containing the less volatile alkaloids, which becomes continually thicker 
an<l of a darker brown colour, and ultimately green by reflected and red- 
brown by transmitted light; — till at length, when the bottom of the 
retort has risen to a red heat, a quantity of spongy charcoal is formed 
and water and carbonate of ammonia escape. Crude bone-oil contains 
about 0*75 p. c. of the more volatile and from 2 to 8 per cent of the 
less volatile alkaloids. (Anderson.) 

2. By distilling piperine intimately mixed with 4 pts. of soda-limOi 
at temperatures between 150° and 160°. (Wertheim,-4nn. Fharm. 70, 62), 
<— Cinchonine distilled with hydrate of potash also yields a number 
of volatile bases, among which picoline is found in small quantity, 
(C. G. Williams, Ed. FhU. Trans, xxi, Pt. 2.) 

Preparation. 1. The oily mixture obtained from bone-oil in the 
manner described for the preparation of petinine (x, 1^0), and dehy- 
drated by means of hydrate of potash, yields between 71 and 100°, a 
distillate consisting chiefly of petinine, then between 132® and 137° prin- 
cipally picoline, and from 151° to the end, chiefly aniline. By repeatedly 
rectifying the distillate obtained between 132° and 137^ and separating 
each time the first and last portions, picoline is obtained in a state of 
purity. (Anderson.) 

2. The oil which passes over in the rectification of coal-tar is shaken 
up with sulphuric acid, to dissolve out the bases and remove the 
naphthalin and the oil which turns brown on exposure to the air; the 
sulphuric acid liquid neutralised with the impure ammonia obtained by 
rectifying the watery distillate of coal tar, and distilled, whereupon there 
passes over with the first portions of water, a dark brown, thickish, oily 
mixture, sinking in water, having an offensive pungent odour, and 
consisting of picoline, aniline, pyrrhol, leucol and a thick heavy neutral 
oil; this oily mixture, together with the supernatant watery distillate, 
carefully rectified, till only one-fourth (containing the heavy neutral 
oil) remains; the distillate, consisting of aqueous picoline and a super- 
natant oil, strongly supersaturated with dilute sulphuric acid, whereby 
its odour is considerably altered; the acid mixture, which gives off all the 
pyrrhol in the state of aqueous solution, distilled; the residue in the 
retort supersaturated with potash, and the distillation continued, whereby 
bases aro obtained, partly dissolved in wi).t9r^ partly floating on the 



PICOUNB. 23a 

snrfaoe in the fona of an oil; the entire distillate left at rest in contact 
with fragments of caustic potash, by the gradual solution of which, the 
picoline loses its solubility in water, and is thrown up to the surface in 
the form of a pale yellow oil containing from 80 to 40 per cent, of water; 
this oily layer remoyed with the pipette, and repeatedly treated with 
solid potash, which must be renewed as often as it gets wet; the oil thus 
dehydrated^ consisting of picoline and aniline, distilled, the receiver being 
changed as soon as a drop *of the distillate turns blue when mixed with 
aqueous chloride of lime (and therefore contains aniline); and the distil^ 
lation still continued, whereby a mixture is obtained consisting of picoline 
and a continually increasing quantity of aniline. The first portion of 

Sicoline which passes over^ is free from aniline, and after being deliy^* 
rated with solid potash, and brought by fractional distillation to the 
boiling point 133*3", is pure. (Anderson.) 

3. Preparation of Odorine, Animine arid Ammoline. — Bone-oil is freed 
from the whole of the watery liquid, and mixed with dilute sulphuric 
acid as long as effervescence ensues; at least an equal quantity then added, 
in order to convert all the sulphates into acid salts; the liquid diluted 
with water amounting to half the oil; decanted after being stirred; shaken, 
and set aside for several hours; then strained through linen, and boiled 
for three hours in a porcelain basm with water renewed as it evaporates 
— whereupon it assumes a dark-brown colour and deposits resin in conse- 
auence of oxidation of the empyreumatic oil; the liquid separated there- 
irom mixed with ^ pt. of nitric acid; evaporated to ^; then brought 
back to its former capacity by addition of water; saturated in a glass 
retort with carbonate of soda, till it scarcely reddens litmus; and distilled 
in a glass retort, as long as the liquid which passes over smells of odorine 
and animine, which toses pass over perfectly free from ammonia. — 
a. The distUlaU is mixed with a quantity of sulphuric acid sufficient to 
remove its odour, then with another equal quantity, in order to form acid 
salts; evaporated in the water-bath till it becomes thick ish; poured 
gradually, so that the heat may not become too great, into a retort 
containing excess of quicklime; and distilled, whereupon anhydrous 
odorine and animine pass over. This mixture shaken up with 3 pis. of 
water, yields, with separation of a large quantity of pure animine, a 
solution containing all the odorine and a little animine. By adding to 
this liquid, a boiling aqueous solution of corrosive sublimate in excess, a 
compound of chloride of mercury with animine separates, even while the 
liquid is hot, as an oil which solidifies on cooling, whereas the compound 
of chloride of mercury with odorine remains dissolved while the liquid is 
hot, and crystallises on cooling. On collecting each of these double salts 
separately, and distilling with potash, animine is obtained from the one 
and odorine from the other. — 6. The liquid remaining in the retort is 
filtered from the resin, mixed while constantly boiling with carbonate of 
soda as long as ammonia escapes, and evaporated with excess of carbonate 
of soda; and the brown oil which then separates, and is a compound of 
ammoline and fusciue, is washed with water and distilled, whereupon the 
ammoline passes over: if not quite colourless, it must be purified by 
redistillation. It then still contains, besides traces of hydrocyanic acid, 
ammonia, odorine and alanine, an oil having a spirituous, radish-like 
odour, soluble in 20 pts. of hot water, and easily volatilised therewith, 
so that all these bodies may be easily removed from the ammoline by 
boiling with water. (Unverdorben.) 



266 BBNZENB: AZO-MUCLBUS C«NH*. 

4. Preparatum of OdorUu, AfUmme. and Olanins, — Dippd's oil ii 
ezActly iieutralised with nitrio aoid till the alkaline reaetion is destroyed; 
the decanted oil distilled in the water-bath, as lon^ as the distillate is solu- 
ble in water, and therefore consists of pare odorine ; and then with a fresh 
receiyer, as long as a mixture of odorine and animine which becomes tnrbid 
on addition of water, passes over, while -^ of the whole remains as a 
mixture of animine and olanine. (Unrerdorben, in Berselius Lekrb, 
Atug, y, 5, 248.) The second distillate, when shaken up with an equal 
quantity of water, separates into animine and an aqueous solution to be 
xurther separated (upwards), and consisting of odorine with a small 
quantity of animine. The residue in the retort, washed with 20 pts. of 
cold water, giyes up to that liquid the rest of the animine, white the 
olanine remains undissoWed. (IJnyerdorben.) 

5. Pure odorine is likewise obtained by passing the yapour of Dippel's 
oil through a red-hot tube, distilling the condensed liquid with 4- V^* ^^ 
hydrate of potash and 6 pts. of water, supersaturating the distillate with 
sulphuric acid, boiling to expel the yolatile oil, and then distilling with 
oxide of lead or oxide of copper, whereupon aqueous odorine passes oyer. 
(Unverdorben.) 

An impure odorine is obtained bj^ distilling oil of hartshorn with 

hpdrate of potash, Ac. — If the odorine is contaminated with ammonia, 

its compound with tartaric acid must be dissolyed in absolute alcohol, 

which leayes the ammonia-salt undissolyed. — To obtain odorine quite 

free from empyreumatic oil, the compound of chloride of copper with 

odorine is prepared (p. 269), and distilled with potash. (Unyerdorben.) 

Compare Beichenbadi's obserrations {Sehw, 61, 404; 62, 46) on Unverdorben's 
methods of preparation, and Unverdorbcii'i obafrratlons in reply. (Sekm* 6ft, 814.) 

Propertiet. Transparent, colourless, yery thin oil, not solidifying at 
0**; of sp. gr. 0*955 at 10°; boiling constantly at 183*3''; baying an obstio 
nately persistent, somewhat aromatic, strongly penetrating, and in the 
dilute state, peculiar rancid odour, and a fiery, sharp taste, extremely 
bitter in the dilute state. Blues litmus, but does not change the ooloor 
of red cabbage. Produces fumes with hydrochloric acid. It does not 
colour firwood or elder-pith yellow when mixed with acids, and remains 
colourless with chloride of lime, unless the presence of pyrrhol produces 
a brown colour. (Anderson.) — Colourless oil, lighter and somewhat less 
mobile than water; does not solidify at -— 25*^; yolatile; produces fumes 
when hydrochloric, nitric, or acetic acid is held oyer it; has a peculiar 
ammoniacal odour, which, after the substance has been purified by prepa- 
ration from its compound with chloride of copper, no longer resembles 
that of bone-oil, but that of Syringa vtilgarie; it is not poisonous, bluM 
litmus, and turns yiolets green« (Unyerdorben.) 

Anderson. 

12 C 72 .... 77*42 77-17 

N 14 .... 15*05 

7H 7 .... 7-53 7-69 

C»NH7 93 .... 100-00 " 

leomeric, therefore, with aniline; it ihoald perhaps be regarded as C'AdH',!!', 
which however presupposes the eiistence of the ttaoletts C^H^ not otherwise koown. 



PIC0LIN8. 267 

DeetmposUions. Piooline does not turn brown or undergo any obange 
in vessels containing air. — 1. Picoline absorbs chlorine gas in considerable 
quantity, deposits colourless crystals of hydrocblorate of odorine, then 
assumes a dark brown colour, and is converted into a resin; and this, when 
suspended in water and further treated with chlorine, yields by distiUa- 
tion, first a crystalline substance which passes over with the water, and 
then another after the water has gone over, (Anderson.)^- Chlorine gas 
passed in excess over picoline, produces thick fumes and a dense yellow 
liquid, from which water (taking up f of the picoline in the form of 
hydrocblorate of picoline, no longer decomposible by chlorine^ precipitates 
a yellow body, from which potash extracts a brownish yellow powder, 
leaving a resin which dissolves only in oil of vitriol or in picoline, 
(Unverdorben.)— -2. Bromine in excess immediately forms with piooline 
a copious reddish precipitate, which, if left over night, collects into a 
non-basic oil insoluble in water, but readily soluble in alcohol and ether. 
(Anderson.)— With iodine and water, picoline forms hydriodate of 
picoline, a brown powder soluble in potaJsh, and an extractive matter 
soluble in alcohol and ether, but insoluble in water. (Unverdorben.) — 
3. Picoline dissolves in nitric acid without any blue coloration, but 
the mixture, when heated, slowly gives off nitrons vapours, and, if evapo- 
rated after long digestion, yields rhombic tables [of nitrate of picoline 1], 
but no picric acid. (Anderson.) — With aqueous chromic acid, it exhibits 
no change of colour, even on boilings but merely yields a small quantity 
of yellow powder. (Anderson.) 

CimbimUiam, Picoline mixes in all proportions with water, bat is 
separated therefrom on saturating the liquid with potash and with many 
alkaline 6alt& (Anderson.) Miscible with water in all proportions^ 
(Unverdorben.) 

Picoline precipitates the hydrochlorates of nranio, stannic and ferrio 
oxide, but is separated from its salts by all basic metallic oxides. 
(Unverdorben.) Fieoline-talts are mostly crystallisable, but do not crys* 
tallise 80 easily or so finely as the aniline-stflts; the best crystals are 
obtained by evaporating the aqueous solutions over the water-bath, 
whereas, on mixing an ethereal solution of picoline with an acid, nothing 
but a semi-fluid mass is precipitated, on account of the smallness of the 
quantity of water present The solutions of picoline-salts decompose 
much less quickly on exposure to the air than the aniline-salts, assuming 
not a rose-red, but a brown colour. (Anderson.) The salts are thick, 
nncrystallisable liquids; they are inodorous, but taste like picoline, 
because that substance is set free by the alkali of the saliva. Those 
picoline-salts which contain a volatile acid evaporate without decomposi- 
tion; those which contain the more fixed acids, give off a large quantity 
of picoline when their aqueous solutions are boiled, and leave syrupy 
acia salts which remain nndecomposed till they are heated considerably 
above 100% and then either give off their picoline nndecomposed, or 
retain it mixed with fnscine. (Unverdorben.)— -Picoline-salts are very 
soluble in water, and some of them are deliquescent (Anderson.) The 
salts, even the tartrate, dissolve in all proportions in absolute alcohol. 
(Unverdorben.) 

The compounds of picoline with carbonic and horacic acid are quickly 
decomposed by boiling with water; those with phosphoric acid are con- 
verted by boiling into acid salts. (Unverdorben.) 



268 BENZBNB: AZO-NUCLBUS C^^H'- 

Sulphite of Ficoline, — Picoline alworbs salphnrous acid gas, with 
BtroDg fumiDg and considerable rise of temperatare^ and forms an oil 
which readily distils without decomposition, dissolves in water in all 
proportions, and is converted into sulphate of picoline on exposote to the 
air. (Unyerdorben.) 

Svlphate of Picoline, — Biacid. — When the colourless mixture of 
sulphuric acid with excess of picoline is evaporated over the water-bath, 
a large quantity of picoline escapes, and there remains a thick oil, which, 
on cooling, solidifies in a mass of transparent colourless plates. This 
mass, when exposed to the air, quickly deliquesces into a transparent 
colourless oil; it dissolves readily m alcohol, but does not crystallise from 
hot alcohol on cooling, and is insoluble in ether. (Anderson.) Anhydrous 
picoline mixes with oil of vitriol, the temperature of the mixture rising 
to ebullition, and forms a colourless oil which is insoluble in excess of 
picoline, and when boiled with water gives off picoline and is converted 
into an acid salt. (Unverdorben.) 

Crystals, Anderaon. 

C"NHy 93 .... 48*69 

2 SO» 80 .... 41'88 41-20 

2 HO 18 .... 9-43 



C«NH7,280» + 2HO .... 191 .... 100-00 
[op rather C«NH80,HO,2SO».] 

Hydiiodate of Picoline. — Picoline forms with iodine and water, in 
addition to other products (p. 267), a liquid which dissolves readily in 
water, altohol and ether; is coloured brown from excess of iodine; and 
when evaporated with water, gives off picoline and hydriodate of 
picoline, and is converted into an acid salt. (Unverdorben.) 

Hydrochlorate of Picoline, — The neutral mixture evaporated to a 
syrup over the water- bath, solidifies on cooling, in amass of prisms, which 
when gently heated, sublime in transparent crystals deliquescing quickly 
on exposure to the air. (Anderson.) Dry hydrochlorate of picoline 
obtained by distilling its compound with chloride of copper, solidifies on 
cooling, in a very deliquescent, tallowy mass, having but little odour. 
By saturating picoline with hydrochloric acid gas, which process is 
attended with nse of temperature and production of fumes, a colourless 
oil is obtained, which volatilises with the watery vapour, and does not 
solidify even at — 25°. 

Nitrate of Picoline. — Dilute nitric acid evaporated to dryness at a 
gentle heat with picoline, leaves a white crystalline mass which, at a 
stronger heat, sublimes in white feathery crystals. (Anderson.) — Nitrate 
of picoline when distilled, passes over, for the most part undecomposed, 
together with nitrate of picoline and a small quantity of ethereal oil, 
and, when the distillation is interrupted, leaves an extractive substance, 
and a resin soluble in potash, together with undecomposed nitrate of 
picoline. 

Picoline forms double Baits with tcrddpride nf antimony and bichloride 
of tin* (Anderson.) 



PICOLINE. 269 

Sulphate of Copper with Pieoline, — Snlphate of copper dissolves in 
anhydrous picoline, with separation of basic sulphate of copper, and 
forms a dark bine liquid, which, when exposed to the air, first gives oflT 
a portion of its picolme and dries up to a green mass, then gradually 
loses the whole of the picoline, and is converted into neutral sulphate of 
copper. From an aqueous solution of sulphate of copper also, picoline 
throws down only a portion of the copper in the form of a basic salt. -— > 
Picoline, whether anhydrous or dissolved in water, has no action upon 
oxide or carbonate of copper. (Unverdorben.) 

Chloride of Copper with Picoline, — A solution of protochloride of 
copper is precipitated by excess of anhydrous picoline, and the brown 
crystalline precipitate recrystallised from boiling absolute alcohol, whereby 
it is obtained in yellowish brown four-sided tables. — They melt above 
100°, being first converted, with partial evolution of anhydrous picoline, 
into a brownish yellow transparent liquid, which solidifies to a black 
viscid tar on cooling, and being finally resolved, with decomposition of 
the still remaining picoline, into hydrochlorate of picoline, together with 
a small quantity of gas and dichloride of copper. With potash, they 
give off perfectly pure picoline free from neutral oil. In contact with 
. water or aqueous alcohol, they are resolved into picoline, hydrochlorate 
of picoline, and basic hydrochlorate of cupric oxide. They dissolve in 
800 pts. of cold and 100 pts. of boiling absolute alcohol. (IJnverdorben.) 

Protochloride of Copper dissolves in anhydrous picoline, forming a 
beautiful blue solution; a concentrated aqueous solution also forms with 
it a clear blue mixture. (Unverdorben.) 

Chloroeuprate of Picoline. -^ A solution of protochloride of copper in 
a small quantity of absolute alcohol, mixed with hydrochlorate of picoline 
(the picoline must be prepared from its compound with chloride of copper 
Dj the action of potash^, and then with ether, amounting to \ of the 
mixture, yields yellowisn crystalline laminss, which must be washed with 
. a mixture of equal parts of alcohol and ether. The laminsQ melt when 
heated, giving off small quantities of water and picoline, and form a 
brownish yellow liquid, which on cooling solidifies in a yellow mass, but 
when further heated, yields hydrochlorate of picoline (which solidifies in 
a tallowy mass), and leaves dichloride of copper mixed with a small 
quantity of charcoal. They turn blue in the air, and give off picoline. 
They dissolve very readily in water, in 6 pts. of cold, and in a much 
smaller quantity of hot absolute alcohol. (Unverdorben.) — When 
aqueous protochloride of copper is evaporated with hydrochlorate of 
picoline, large rhombohedral crystals are obtained. (Anderson.) 

Chloride of Mercury with Picoline, — Picoline immediately forms a 
curdy precipitate with a concentrated solution of corrosive sublimate, 
and separates silvery radiating needles after a while from a dilute solu* 
tion. These needles give off picoline when dried by heat; also when 
boiled with water, a white powder being at the same time precipitated. 
They dissolve sparingly in cold, more readily in hot water, easily in 
dilnte hydrochloric acid, forming a peculiar compound [doubtless the 
following], and in hot alcohol, crystallising therefrom in needles and 
feathers. (Anderson.) -— Picoline added to aqueous corrosive sublimate 
throws down a white crystalline powder, which smells of picoline, dis* 



270 BfiNZBNE : A20.NUGLBUS C"NH*. 

fiolves in 10 pts. of boiling wacer^ and also in warm alcohol and ether, 
cnrstallifiing out for the most part on cooling; when heated alone, itgiYes 
off, first piooline, then corrosive sablimatOi and its aqueous solution when 
boiled, gives off picoline, and is converted into solution of corrosive 
sublimate; when heated with potash, it is resolved into picoline which 
escapes, mercuric oxide which is precipitated, and chloride of potassium* 
(Unverdorben.) 

Air^dried, Andermm, 

12 C 72-0 .... 19-79 2051 

N 14-0 .... 3-85 

7 H 7-0 .... 1-92 2-19 

fl HgCi 270*8 .... 74-44 

C«NH',2HgCl 363-8 .... 10000 

Chlaratnereurate of Ficoline, ^^ Deposited as a transparent colourless 
oil permanent in the air, when an aqueous solution of corrosive sublimate 
is boiled down with hydrochlorate of picoline. (Unverdorben.) 

Picoline does not precipitate nitrate of silver. (Anderson.) 

Chloride of Oold with Picoline, — Picoline added to aqneons terehlo- 
ride of gold throws down a lemon-jellow powder, which dissolves in a 
large quantity of boiling water, and crystallises therefrom in delicate 
yellow needles. — The yellow powder melts below 100°, forming a clear 
yellow glass, and when more strongly heated, gives off hydrochlorate of 
picoline, leaving gold together with a few other products of decomposi* 
tion; it is slowly decomposed by boiling nitric acid; quickly by aqueous 
potash, yielding chloride of potassium, free picoline, and a precipitate of 
auric oxide; it is nearly insoluble in oold water, sparingly soluble in 
boiling water, and precipitates as a granular powder on cooling. 
(Unverdorben.) 

Chloroaurate of Picoline. — Precipitated on mixing a solution of gold* 
with hydrochlorate of picoline, in delicate yellow, inodorous crystals, 
which redden litmus. These crystals, when heated alone, melt, give off 
chlorine and hydrochlorate of picoline, and leave gold. With the smallest 
quantity of potash, they immediately give out the odour of picoline. 
They dissolve in 20 pts. of boiling water, and in hot aqueous sulphuric, 
hydrochloric or nitric acid, crystaSising out again for the most part on 
cooling. They dissolve in alcohol more readily than in^ ether. (Unver- 
dorben.) 

Chloride of PUUinum with Picoline, — Resembles the compound of 
chloride of gold with picoline; from a boiling aqueous solution it is preci- 
pitated as a powder on cooling. (Unverdorben.) 

Chlorophtinctte of Picoline* — A concentrated mixture of bichloride 
of platinum and hydrochlorate of picoline yields immediately, and a 
dilute mixture after 24 hours, orange-yellow needles, 'which may be puri- 
fied from excess of picoline by recrystallisation from a hot solution of 
bichloride of platinum containinff hydrochloric acid, and washins with 
alcohol and ether« -* Orange-yellow slender needles, which dissdve in 



PlCOLfNS. 271 

ahoat 4 pis. of boilinff watery and readily also in alookol. (ABdenon.) — 
Yellow crystals soluble in 4 pts, of water. (UnverdorboD.) 

Anderson. Wertheim 

Dried at 100*. (Jlrfm jtiperM), 

12 C 72«0 .... 84*06 M'0» .... 23-89 

N 140 .... 4-68 

8 H 8-0 ..,. 2-68 .. 3-05 .... 2-94 

Pt 990 .... 3309 32*53 .... 32-63 

3 CI 106-2 .... 35-49 

CONH8Cl.PtCl* 299-2 .... 10000 

%. PloHnapiMlini. C»NH«PtttC«NH»Pt«..— Chloirolatinateof pico- 
line is decomposed by boiling in the same manner as cnloroplatinate of 
pyridine (z, 407)} bot more slowly, the decomposition not being oomplete 
till after 8 or 10 days; the addition of a small quantity of picoline, how- 
erer^ accelerates the action, causing it to be completed in a few hours. 
The product is the tfihydrocfdorale of picoline \ 

CWNH8Cl,PtCP - C"NH»Pt,2HCl + HCL 

This salt is insoluble in water. It unites with chloroplatinate of picoline, 
forming the compound C"NH»Pt,2HCl + C»NH«C1, PtCl", which crj^s- 
tallises in granules, but is much less soluble than the corresponding 
P3rridine compound. (Anderson, Ann. Pharm, 96, 203.) IT. 

Picoline dissolyes readily in ufood^tpirU (Anderson), alcohol and ether 
(Unyerdorben.) 

AcdaU fif Ficolin$. — May be distilled with watert (Unrerdorben.) 

Oupro-AeetaU qf Pieoline, — The dear blue solution of cupric acetate 
in not too large a quantitjr of aqueous picoline, deposits, when eznosed 
to the air, a basic salt in grass-green-crystals, which smell faintly of 
picoline, do not giro off that base on exposure to the air, dissolve readily 
m water and alcohol, but are insolable m ether; their aqueous solution 
when distilled, gives off, first picoline and then acetate of picoline^ 
leaving acetate of copper with excess of oxide. -— If the picoline is in 
excess in the bine solution, water and acetate of picoline volatilise, and 
rectangular prisms are formed which do not redden litmos, eflSbresce 
slowly in the air, dissolve readily in water and alcohol, but not in ether, 
and when boiled with water, decompose in the same manner as the green 
crystals. (Unverdorben.) 

Oxalate of Puioline. — Aqueous oxalic aeid mixed with excess of 
picoline and evaporated over lime, forms tufts of needles, and finally 
solidifies in a dense crystalline mass, which dissolves readily in water and 
in alcohol, either aqneous or absolute. It melts at 100^ giving off large 
quantities of picoline vapour, and leaves on cooling a thick liquid, which 
slowly deposits slender needles, probably consisting of the acid salt. 
(Anderson.) 

ButyraU ofPieolme, — 0'd which may be distillecL (Unverdorben.) 



272 BENZENB: A20-NUCLBUS C»NH*. 

Picoline mixes readily with volatile oils (Unyerdorbeii), and with Jixed 
oils, rAnderson.) It dissolves several resins which are separated there- 
from oy boiling nvith water. (Unverdorben^ With infusion of gaU-nuts 
it forms a pale yellow curdy precipitate. With several kinds of extrac- 
tive matter, it u>rms compounds which are not decomposed by boiling with 
water, but readily by potash. (Unverdorben.) It does not coagulate white 
of egg (Anderson); with equal quantities^ ceagulation takes place in a 
quarter of an hour. (Wertheim.) 



% Ethylopicoline. 

CP'NH" = C*H*,C»NH' = C«N(C*H»,H«). 
Anderson. FhU. Mag, J. [4], 9, 214; Ann. Fharm. 94, 861. 

Formed by the action of iodide of ethyl on picoline. When 1 vol. of 
anhydrous picoline is mixed with 2 vol. iodide of ethyl, and the mixture 
heated in a sealed tube placed in the water-bath, an action takes place 
attended with considerable evolution of heat, the liquid becoming turbid 
and separating into two layers, the upper of which solidifies in a crystal* 
line mass of hydriodate of ethylopicoline. With the aid of heat, the 
action is complete in about ten minutes; it also takes place at ordinary 
temperatures, but then occupies several days. The hydriodate Lb recrys- 
tallised from a very small quantity of boiling alcohol and ether. 

Hydrated Oxide of Ethylopicoline is obtained by treating the solution 
of the iodide with moist oxide of silver, and quickly separating the liquid 
from the resulting iodide of silver. If the action be too long continued, 
and especially if heat be applied, further decomposition takes place, 
and the liquid assumes a violet or crimson colour. — The filtered uqnid 
is colourless; has a caustic taste and strong alkaline reaction; absorbs 
carbonic acid from the air; precipitates and redissolves alumina; precipi- 
tates corrosive sublimate; and exhibits generally with metallic salts the 
same reactions as potash or soda. When boiled, it assumes a deep red 
colour, and emits an odour of ethylamiue, which base is more abundantly 
evolved on boiling the liquid with potash. The solution is partly decom- 
posed by evaporation in vacuo, and leaves a hard gummy mass, which 
dissolves in water with blood-red colour. The formation of a fixed base 
by the action of oxide of silver on the hydriodate of ethylopicoline seems 
to show that picoline is a nitrile-ba«e, like triethylamine, &c 

Hydriodate C"NH",HI = C»N HXC*H»), I. — Crystallises from a 
mixture of alcohol and ether, in tabular crystals having a silvery lustre. 
Melts below 100°, forming an oily liquioL Dissolves yery readily in 
water and alcohol, sparingly in ether. On treating the aqueous solution 
with a considerable quantity of potash, the hydriodate is deposited in the 
form of a thick oil, which gradually concretes into a crystalline mass. 
When boiled with strong potash, it gives off a volatile alkali 

Anderson* 
16 C 96 .... 38*70 38-57 

N 14 .... 6-67 5-61 

12 H 12 .... 4-83 4-93 

I 126 .... 50-80 60-89 



C>«NH»I 248 .... 100-00 ........ 100-00 



ANIMINB. 273 

CAZoro-attrot^. —- Prepared by decomposing the hydriodate with 
nitrate of silver^ precipitating the excess of silver from the filtrate with 
hjdrochlorio acid, and adding a concentrated solution of terchloride of 
gold: the salt is then gradually deposited in golden-yellow flattened 
prisms, which dissolve sparingly in cold, readily in hot water; bnt are 
insoluble in alcohol and in ether. 



16 C 

N 

12 H 


96-0 

14-0 

12-0 

199-0 

141*6 


.... 20-83 
.... 3-06 
.... 2-60 
...• 42-69 
.... 30-82 


Anderson. 
....... 20-59 

2-75 


Att 




4 CI 








C»NH»Cl,AiiCP.. 


462-6 


.... 100*00 





CTUaraplatinate, — Prepared as the gold-salt Separates gradually in 
onuffe-red tabular crystals* Dlssolres readily in water, but is decom- 
posed when its aqueous solution is boiled for some time. 



16 C 96*0 

N 14*0 

12 H 12-0 


.... 29-33 
.... 4-31 
.... 3-66 
.... 30*16 
.... 32*54 


.... 29-15 

.... 3*76 
.... 29*75 


Anderson. 

.••• £9 /o .... 




Vt 99-0 

3 a 106-2 


29*91 






CWNHMCl,PtCP .... 327*2 


.... 100-00 









AlhoMds resembling Pieoline, hut le$8 volatile and les$ soluble 

in water, 

DiBooyered, together with piooline, in bone-oil, by Unverdorben in 1827, and pre- 
pared in the manner already described (pp. 265, 266).— [More recently, Anderson has 
discovered in bone-oil, two alkaloids homologous with pieoline, but less volatile, viz., 
Lftiidine C^^NH*, and Collidine C^^NH". The animine, olanine, and ammoline 
obudned by Unverdorben were probably mixtures of these two bases, in various pro- 
portions, and with other substances in addition.] 



1. Animine. 

Colourless oil, less volatile than pieoline; its aqueous solution changes 
the colour of reddened litmus to violet 

Animine dissolves in 20 pts. of water. The solution becomes turbid 
when heated, and deposits animine, which redissolves on cooling. 

With acids animine behaves like pieoline and has about an equal 
degree of affinity for them. 

WiUi oil of vitriol it combines, with great rise of temperature, and 
forms an nncrystallisable oil, which, when boiled with water, gives off 
ammonia, and is converted into an acid salt, not further decomposible by 
concentration. This acid salt dissolves in any quantity of water or 
alcohol, and likewise in the peculiar ethereal oil contained in Dippel's oil, 
which is soluble in 65 per cent, alcohol. 

TOL. XI. V 



274 BENZENE: AZO-KUCLBUS C^^NH*. 

Gorfodre sublimate fonn0 with hydroohlomie of anhniiM, a colourless^ 
oily, neuttal double salt; on mixing animme with excess of hot aqtoeoas 
corronTO sublimate, a compound ofmercnric chloride with animine sepa- 
:^ates in the form of a yellowish oil| which becomes hard and brittle on 
cooling, a|id when boilea for some time with water, is resolred into animine 
which volatilises, and corrosiye sublimate which remains dissoltred. 

With gold-solution, hjdrochlorate of animine forms a brownish-yellow, 
oilj double salt; and with platinum-solution, a crystallisable double salt 
sparingly soluble in water. 

Benzoate of animine is oilj, sparingly soluble in cold, more readily in 
boiling water, and on account of the inferior yolatility of animine, is less 
easily decomposed by boilihg #ith water than benzoate of picoline. 

Animine dissolves in aU proportion^, in alcohol, ether, and oils. A 
mixture of animine and picoline slowly dissolves copal; and when the 
somewhat thickened solution is boiled in a retort with alcohol of 30 per 
cent., the whole of the picoline passes quickly over, together with a small 
quantity of animine;^ and leaves in the alcoholic water, a light-coloured 
oil, which is a compound of copal with pure animine* This coinponnd is 
easily decomposed by potash; giVes np only pati of its animine to aqtieous 
acids; but if it be previously djssolved in alcohol of 65 per cent., hydro- 
chloric acid precipitates the whole of the copal, and pure hydrochlorate of 
animine remaind m solution, (Unverdorben, Fogg, 11, 59 and 67)* 



Hi Olanine. 

Colourless oil, heavier than water; smells like animine, but less 
stronffly, also like aniline, not unpleasantly; blues litmus but very feebly. 

Slowly turns brown on exposure to the air, a 6mall quantity of fiiscine 
being formed at the same time. 

Olauitie is bnt tery slightly soluble in Water. It decomposes the 
same metallic salts as picoline, and combines t^ith kbiiB, forming salts 
resembling tbose of picoline, but not crystallisable; they are decomposed 
by the same bodies as the picoline-salts. 

Hydrochlorate of olanine forms with hydrochlorate of ferric oxide, a 
dark brown, oily double salt, which is not decomposible by acids; and 
dissolves readily in 2 parts of cold water, but requires 4 pts. of boiling 
water to dissolve it; so that the cold solution when heateid, deposits an 
oil which redissolves on cooling; it likewise dissolves in oil of cummin, 
forming a solution which is not decomposed by boiling. 

Hydtochlorate of olanine behaves with corrosite sublimate like 
hydrochlorate of animine. — When an aqueotis solution df corrosive sub- 
limate ins ihited With pure olanine, a yellow resinous precipitate is formed, 
which is iiot decomposed by boiling with water (thereby affording a dis- 
tinction between olanine and animibe), dissolves in 1000 pts. of boiling 
water, whence it is precipitated in the crystalline state on coolin|f, bnt is 
insoluble in alcohol (also a distinction between olanine i^nd animiiie). 

With hydrochlorate of auric oxide, hydrochlorate of olanine forms H 
yellowish-brown, oily double salt, which is heavier than water, not ddcoiu- 
posible by acids; deposits a small quantity of gold when boiled fdl* ddtne 
time with water; dissolves sparingly in cold, more freely in boilibg water, 
and in any quantity of alcohol or etheh — Free olanine forms with 



IODANILlNB« 275 

hjdrbishlomt^ of anrio otide, a brown, hatd, bttlo double Bali, wliioh It 
aoloble in alcobol, intolnble in watet^ and ia transfonned, yeiy slowly by 
boiling with hjdroohlorio aoid, but very eaolj on addition of alcobol^ 
into do oilj neutral double salt With hydroohlorate of platinio oxide^ 
ohuiine forms a tarry double salt^ which dissolTee readily in water and 
aleohol, but not in ether. 

Olanine dissoWee easily and in all propoftielM in alcohol and eihof* 
(Unverdorben^ Pegf^. 11 f 69.) 



3. Ammoline. 

Colourless oil, heavier than water, boiling at a point very near that 
of the filed oils, and consequently distilling over but sparingly with water; 
blues litmus tery strongly. 

By chlorine, it is completely resolred into hydrochlorate of ammoniai 
auimitie, fnsolne, and an extraetire matter. 

Ammoline dissolves in about 200 pts. of cold and 40 pts. of boiling 
water; the solution may be concentrated by boiling without much loss. 

At the boiling heat, it expels ammonia from the aqueous sulphate and 
hydrochlorate; forms with acids, uncrystallisable salts, which yield but 
little ammoline when boiled with ammonia. 

The borate, sulphate, hydrochlorate, nitrate, acetate and succinate of 
ammoline are not crystalusable; they dissolre in any quantity of water 
or alcohol, but are insoluble in ether. — - The hydrochlorate ana acetate of 
ammoline may be distilled almost without decomposition. — The nitrate 
decomposes wnen heated, in such a manner that part of the ammoline is 
destroyed, and the rest passes over in the free state.-— With heayy 
metallic salts, ammoline forms double salts similar to those of olanine. 

Ammoline mixes in all proportions with alcohol and ether, and com« 
bines yery intimately with many resins and eztraoUye matten. (Unyer- 
dorben, Fogg. 11, 74.) 



AfsoUodine^ucteui C^NIR*. 

Iodaiiiline« 

C^NH'l = C^NIHMP. 

A. W. HoniAiQl. (1848.) Ann. Pham. 67, 04; CKeHL Soc. Qu. J. 
1, 271. 

ForwMttiofi. By the action of iodine or iodide of qranogen on anilint 
(pp. 861, 853). 



iV^tfnUiofi. \\ pi of iodine is gradually disiolyed in 1 pt of 
aniline; the solntion mixed with hydrochloric acid of sp. gr. 1*11 (a 
stronger acid would separate part of the h^rochlorate of aniline); the 
solution of hydrochlorate of aniline^ hydnodio aoid, Ac, separated by 

t 8 



itie BENZENE : AZOTIODTNE-NUCLEUS CVNIH*. 

filtration from the precipitated and still stronglj coloured b^drocblorate 

of iodaniline, which is sparingly soluble in water; the precipitate washed 

seyeral times with hydrochloric acid, and crystallised sereral times from 

boiling water, at last after boiling with animal charcoal, till the crystals, 

which are at first ruby-coloored and contain free iodine^ together with a 

brown induretted decomposition-product of aniline, are completely 

decolorised; and the iodaniline precipitated from their aqueous solution 

by ammonia^ as a white crystalline powder, which — in order to free it from 

any of the yellowish decomposition-product and phosphate of lime from 

the animal charcoal, that may still adhere to it — is dissolyed in alcohol, 

filtered from the yellowish product, and precipitated by water in the form 

of a white crystalline mass. — The liquid filtered therefrom yields hj eraporfttion 
jeUowtBh 0U7 drops which crystallise on cooling. 

Properties. White crystalline powder, which crystallises from the 
solutions in prisms and needles, neyer in octohedrons; the mass solidified 
from cooling also neyer exhibits the cleayage-fiftoes of the octohedron. 
Heayier than water. Melts at 60^, forming a yellowish oil, and at the 
moment of solidification, shows a temperature of 51°, but sometimes 
remains liquid eyen at the ordinary temperature, in which case, contact 
with a glass rod often causes it to solidify suddenly in a crystalline mass. 
When eyaporated at a rather strong heat, it yolatilises undecomposed, 
and easily distils oyer eyen with yapour of water. Has a yinous odour 
and a burning aromatic taste. Has no action on yegetable colours. 
Like aniline, it imparts a deep yellow colour to fir wood and elder-pith; 
but chloride of lime colours it, not yiolet but reddish. 

Hofmann* 

12 C 72 .... 3303 33-08 

N ^ 14 .... 6-42 

6H 6 .... 2-75 2-83 

I 126 .... 57-80 57-87 

CWNH«1 218 ... 100-00 

DtoompoMons, I. The yapour hums with a bright sooty flame. — 
2. In contact with the atr, iodaniline becomes quickly coyered with a 
brown, metallically lustrous film, and gradually assumes a black colour 
extending throughout the whole mass. — 3. Cfdorine decomposes iodani- 
line into terchloraniline, terchlorocarbolio acid (as with aniline, p. 250), 
and chloride of iodine. — 4. With bnmUne, alcoholic iodaniline solidifies 
in the form of crystalline terbromaniline, while all the iodine is set free 
as bromide of iodine. — 5. Chlorate of potash with hydrochloric acid 
forms, as with aniline, terchlorocarbolio acid and chloranil.*— 6. With 
Itrong boiling nitric acid, iodaniline forms, with brisk action and eyolution 
of iodine-yapour, a solution from which picric acid crystallises on cooling. 
— ?• Crystallised chromic acid decomposes iodaniline with yiolence, but 
does not set it on fire. — 8. Gently heated potassium decomposes iodaniline 
with yiolence, forming iodide and cyanide of potassium. •— Potassium- 
amalgam introduced into aqueous nitrate of iodaniline, immediately forms 
iodide of potassium, and reproduces a small quantity of aniline, whilst the 
greater portion is conyerted into a yellow crystalline substance haying an 
aromatic odour. Zinc immersed in iodaniline supersatured with sulphuric 
acid, eliminates iodine and aniline, so that after a few minutes the liquid 



lODANlUNE. 277 

foims a blue oolonr with starchy and after sataration with potash, gives up 
aniline to ether. -— 9. When chloride of cyanogen is passed through 
iodaniline dissolved in ether^ hjdrochlorate of iodaniline is first precipi- 
tated bat afterwards disappears, and the iodaniline is converted into a 
transparent, slowlj crystallising resin^ which is a mixture of hjdrochlorate 
of biniodomelanilme and iodaniUne-urea. Formation of hjdrochlorate of 
biniodomelaniline : 

2Ci«NHn + C«Na = C?*N»H"P,Ha ; 
Formation of iodaniline-orea and hjdrochlorate of iodaniline: 
2C»NH«I + (?NCl + 2H0 - C"N«H7I0« + C»NH«I,HCL 

Ccmbina^ons, Iodaniline dissolves very sparinglj in cold water, and 
crystallises from boiling water in interlaced hairs. 

It dissolves in hinUphide of carbon. 

Iodaniline is a weaker base than aniline, and is therefore precipitated 
bjanilinei and precipitates onlj alumina^ not oxide of zinc or sesquioxide 
of iron. The Salts of Iodaniline crystallise as readily as the aniline- 
Baits, and are generally less soluble. 

Sulphate of Iodaniline, — White shining scales^ containing 19-24 p. o. 
HO,SO^ and therefore = C»NH»I,HO,SO»; sparingly soluble in cold, 
more soluble in hot water; the solution when boiled deposits a product 
insoluble in boiling water. 

Hydriodate of Iodaniline, — Radiated crystalline mass^ easily soluble 
in water and quickly decomposing. 

Hydrohromate of Iodaniline, — Very much like the hydrochlorate. 

HydroMorate of Iodaniline, — Crystallises from boiling water in 
nacreous laminee and thin needles. Contains 14*44 p. c. hydrochloric acid. 
Dissolves sparingly in cold water, and is precipitated therefrom almost 
entiiely by strong hydrochloric acid; dissolves in alcohol but not in ether. 

Nitraie of Iodaniline, — Crystallises from hot water in long capillary 
needles. The salt does not precipitate silver-solution; it dissolves both 
in cold and in hot water better than the other salts of iodaniline, and 
readily also in alcohol and ether. 

Iodaniline forms with sulphate of copper a yellowish precipitate, pro- 
1>ably a double compound. 

With terchloride of gold, hydrochlorate of aniline forms a scarlet prfr^ 
cipitate, which quickly decomposes. 

Chloroplatinate of Iodaniline. — The orange-yellow crystalline pre- 
cipitate formed by hydrochlorate of iodaniline m bichloride of platinumi 
is easily pnrified by washing with ether. 



12 


72-0 


.... 16-97 .. 
.... 3-30 

1-65 .. 
.... 29-70 

a... ^O 04 «. 

.... 25-04 


Hoftnaim. 
16-82 


N 


14-0 




7 U 


70 


1-87 


I 


1260 




Pt 

3 CI 


990 

106-2 


23-14 









C^UaCl,PtCP . , 424-18 .... 100-00 



278 BBNZENB: AzOBROMINS-KUCLEUS Ci^NBrH^. 

Oxalate of lodaniline, — Long flat needles oontainSng 17*30 p. e. 
C*H«0*, and therefore = 2C»NHn,C*HH)*. T)iey diasolre eparingly ia 
water and alcohol, hat are iasolable in ether. 

lodaniline dissolves in wood-spirit, alooMp eAer^ aceUn^f and ia 
hoth Jtxfid and pdatUe, (Hofmann.) 



Az6bromine^ueleu8 (PNBrH^ 

BromaniUne. 

C«NBrH« = C»NBi*,H». 

HoFMANN. (1845.) Ann, Phaim^ 63, 42. 

Fofmaiion. By iieatiDg brrauMtipe with pptiiht 

Preparation, Bromisatine is distilled with strong pota^AiJey till th« 
residue is nearly dry, and gives off, together with ammonia, a brown oil 
which no longer solidifies; and the oily drops which passed over at the 
beginning of the distillation,- and have solidified in the crystalline form, 
ai« washed with wftter on a filter, ^d recrystallised from boiling alcohpL 

Properties, Colourless, regular octohedrons, exaetly like chioraniline, 
melting at 50° into a violet oil, which in solidifying sinks to the tempe- 
rature of 46°; in odour and taste it resembles chloraniline. 

Hofintim. 

12 C 72 .... 41-8« 42-45 

N 14 .... 8-14 

« H B .... 3-49 ........ #7i& 

Br ...r,r.... 80 ..., 46-51 

"c^^H^Br ............... 172 .... lOQOO '' " 

BwiBinilitte is easily leduoed to aniline by pot«ssinm-^malgam (Ann, 
Pkarm. 67, 76). — With excess of bromide of pthyl, it i^ /juickly cf^ 
verted ioAa hjimbfoamte of ethylobronuui^lin^; 

C»NBrH« + C<H«Bp - C»VBrH»,HBr. 

Its aqueous sdatleB imparts a violet eoloar to aqueous chloride of livcL 
weaker than that produced by aniline, bat etrongsff than that p^xidaeed 
by chloraniline. Its salts colour chloride of lime red-brown and fir wood 
yellow. Bromaniline dissolves readily in bisulphide of carbon. 

Hydrochlorate ef Bromaniline. — CrystalliBes from boiling water iu 
nacreous radiated fibres, but, by evaporation over oil of vitriol, in well 



BIBBOMAVILIMS. 879 

OMoroplaiinaie of AvmantMw. -r Precipitated op mixing bydro- 
chlorate of bromaniune with bichloride of platinam; closely resembles 
the eorre^ponding compound of cbloraailine; eoBtoins 24'10 p.o. platiaum. 
and is therefore C"NH«Br,HCl + PtCP. 

Oxalate of Bromaniline, — The crystalline powder precipitated from 
alcoholic bromaniline by aqneons oxalic acid, is collected on a filter and 
crystallised from boiling water. Indistinct crystals, sparingly soluble in 
water and alcohol. (Hf^nuuin.) 

Air-dried cry9tal9r Hofmaxm. 

28 C 168 .... S8-71 38-93 

2 N 28 .... a*45 

14 H 14 .... 3 23 3-34 

2 Br ,., 1)50 ..., 36-86 

8 O ' 64 .... 14-75 



■^" 



2C»NH«Br,C*H»08 434 .... 100-00 



4spbremine'fnideu8 O^NBi^H*. 



Pibronwulipe. 

HoFMAMN. (1845.) Ann. Pharm. 53, 47. 

Preparation, Bibromisatine is distilled with hydrate of potash, the 
distilled and crystallised pil freed frpm ammonia hy washing with water, 
and crystallised from boiling alcohol. 

Properties, h^gfip 0^t> #omew^a|; rhombic prisms, melting between 
50^ ana 60^^ into a iark-coloured pil^ which often remains liquid long 
after cooling, but then crysjt^U^ suddlenly pn agitation. 

12 C 7» .... ^8-68 .„..,,, 28-77 

N.,.. ..,,.,, ,..,... 14 ..,, 5-68 

5H 5 .... 1-99 2-40 

2 Br 160 .... 63-75 

• : — :— : ^ 

C«NH«Br» 26J .... lOO'jOO 

R 

BibrovnaniUoa dissolves spariogly in boiling mUer, fornung a liquid 
which becomes turbid pn oooling ana gra4uaUy deposits slender needles. . 

It is a very weak baae; its solution in acids colours firwood yellow; it 
is preoipitated by alkalis. It forms crystallisable salts, which howe?er 
are less stable than those of bromaniline. 

The solution of bibromaniline in boiling hydrochloric acid, yields on 
cooling, laminsB containing 13*31 p. c. hydrochloric acid; when they are 
dissolved in water, part of the base separates in thin oily drops; and the 
solution evaporated under a bell-jar over limp, which abstracts the^reater 



280 BENZENE s AZOBROMINE-NUCLEUS C^^NBims. 

part of tbe hydrochloric acid^ deposits nearly pare crystalline 
bibromaniline. 

The hydrochloric acid solution forms a crystalline orange-yellow 
precipitate with bichloride of plaHnum, 

Bibromaniline is solnble in alcohol. (Hofinann.) 



Atdbromin&^udeus (PNBr*H*, 

Terbromauiline. 

(PNBr^H* = C»NBr»H«,H». 



Fbitzbchb. (1842.) J. pr. Chenu 28, 204. 
A. W. HoFMANN. Ann. Fharm. SB, 50. 

BronumUM (Fritsdie). 

Preparation. 1. Dry bromine is mixed with aniline in such pro* 
portion that the mixture solidifies completely after a while in the 
crystalline form^ after which alcohol is adaed, and also more bromine till 
its odour becomes permanent The greenish-grey crystalline magma of 
tolerably pure terbromaniline is then separated by filtration from the 
greenbh-yellow alcoholic liquid, which contains hydrobromic acid and 
the decomposition-products of the alcohol^ and deposits more terbromani- 
line when mixed with water; after which it is washed on the filter with 
alcohol, and dissolved in hot alcohol: the solution thus obtained yields 
nearly colourless crystals. (Fritzsche.) — 2. Tbe aqueous solution of an 
aniline-salt is mixed with aqueous bromine, which disappears and produces 
a white turbidity and precipitation of microscopic needles, the addition of 
bromine beinff continued till the precipitation ceases and a slight odour of 
bromine remains; the precipitated powder, which has a reddish tint arising 
from a decomposition-product, collected, and freed from this impurity by 
distillation in a small retort; and the distillate, which solidifies in a crys- 
talline mass, recrystallised from boiling alcohol. (Fritzsche.) — 3. An 
aqueous solution of hydrochlorate of bromaniline is mixed with aqueous 
bromine, the yiolet-white precipitate distilled with water, whereby snow- 
white crystals are obtained at first, but afterwards violet crystals which 
cannot be decolorised by recrystaUisation from alcohoL (Hofinann.) 

Properties. Crystallised from hot alcohol, it forms colourless, shining, 
long, slender needles; but when solidified after fusion, it is of a crystu- 
line texture, brittle and easily pulverised. Melts at 1 17^ into a clear 
liquid; boils at about 300^; distils over unchanged (Fritzsche); and sub* 
limes in radiating crystals having a silky lustre, (nofmann.) 

I Fritncbe. Hofmann (coUmred.) 

12 C 72 .... 21-82 2205 2316 

! N 14 .... 4-24 4-72 



4H 4 .... 1-21 1-21 1-51 

3 Br 240 .... 7273 71*80 

C^NH^Br* 330 .... lOO'OO 9978 



CHLORANILINB* 281 

DecompagUions. 1. Strong boiling nUrie aetd decomposes terbrom- 
aniline. -— 2. Wann oil of vitriol dissolves it without decomposition, 
acquiring a pnrple colour nrom decomposition only when heated nearly to 
the boilinff point Strong boiling potash-ley has no action upon iL 
(Fritische.) 

OomtnnatiaiM, Insoluble in water. ^Fritische.) 

Terbromaniline dissolyes abundantly in warm oil ofifitriol, separating 
uncombined on coolings and is precipitated in the crystalline state by 
water. (Fritzsche.) 

It is not basic, and does not dissolve either in dilute acids or in 
alkali& (Fritzsche, Hofmann.) 

It dissolves sparingly in cold, readily in hoUing aloohol and in ether^ 
(Fritzsche.) 



Azochlorifne^wUw (?'NG1H^ 

Ghloraniline, 

C"NC1H« = C»NC1H*,H». 
A. W. Hofmann. (1845.) Ann. Fharm. 53, 1. 

Preparation, Chlorisatine is distilled with potash-ley or hydrate of 
potash, till the residue has become solid, gives off ammonia together with 
the hydrogen, and yields a blue sublimate and a brown oil which no 
longer solidifies on cooling. The solidified oil which first passed over is 
then collected on a filter, freed from ammonia by water, and crystallised 
from boiling alcohol. 

Properties, Octohedrons having a diamond lustre, heavier than 
water, melting between 64° and 65°, into a yellow oil which solidifies at 
57° in large octohedrons. Evaporates even at ordinary temperatures, so 
that hydrochloric acid held over it produces fumes; may be easily 
distilled with water; boils by itself at a temperature above 200°, and 
with some decomposition, so that, together with the oil, the above-men- 
tioned blue product passes over. Has an agreeable vinous odour and an 
aromatic burning taste like that of aniline. Does not act upon red litmus 
or turmeric, but turns dahlia fiowers green, 

Air'dried eryaidU, Hofmann. 

12 C 72-0 .... 56-51 66-19 

N 140 .... 10-99 11-38 

6H 60 .... 4-71 5-02 

CI 35-4 .... 27-79 27-45 

C»«NC1H« 127-4 .... 100*00 100-04 

DecampoaUions* 1. Chlorauiline hums with a bright, stronj^ly 
fuliginous flame, having a bright green border. — 2. Chlorine together 



282 BENZENE : AJZOCKLOBUrB^^MUCLEUS CUNaH«. 



with wi^y eoDTerto AlofMiiUafi, paiily iiita tercbloraiiiiuie, putly into 
ten^lorooarbolic Mid: 

and: 

C»NaH« + 4Q + 2Hp - C»Cl»H»p» + HQ + NH<a. 



9. Bromine^ aitheF aahydioiis or hjiialedi deaonpoMs 

with gnat evolation of faeal^ foiq^g bibronoofalonailiao tmi liydno* 

bromicacid: 

C"NC1H« + 4Br - C«NClBr«B* t ?HBr, 

%. Heated with strong niiric aeid, it begine to boil and continues boiling 
even after removal from the fire; gives off nitrous acid; and yields, first, a 
dark red, then a black opaqne liquid, and afterwards, as the heating is con- 
tinued, a clear scarlet solution, which does not precipitate nitrate of 
silver, and on cooling, yields, sometimes golden-yellow needles resembling 
picric acid, and probably conatsting of bmitrochloroctebolic acid 
C^X*C1H',0', sometimes a resin, which is precipitated by water in yellow 
flakes, and dissolves with deep yellow colour in alkalis, alcohol and ether; 
the solution of this resin in alkalis is precipitated by acids, and its ammo- 
niacal solution, when freed from excess of ammonia by boiling, precipi- 
tates silver solution reddish yellow, sometimes also in yellow crystalline 
spangles. — 5. The aqueous solutioii of cblor^niline acquires a very faint 
violet tint when treated with chloride of lime. — 6. With chlorate of 
potash and hydrochloric acid, chloraniline forms a violet-red, then a turbid 
brown, and ultimately a colourless liquid, which at first deposits crystal- 
lising chloranil, together with ter- or quintochlorocarbohc acid, m the 
form of a brovm viscid substance soluble in alcohol^ but after decoloration 
contains nothing but chloranil and sal-ammoniac; the same paction 
therefore as with aniline: 

CMNCIH* + 4C1 + 2H0 = C"C1»H»0» + NH*C1 + HQ; 

t^prcblorocarbolic 
acid, 

farther: 

j^aintocUoro- 
MfhoUcscid. 
andi 

C»«NaH» + 6C1 + 4a - CaCl«0* + NH<a + «HOI. 

chloraniL 

7. The crystals, immersed in aqueous chromic iisid tum brown and 
become resmised; the dry pfiixture takes fire at the melting point of 
chloraniline. — 8. Aqueous chloraniline inAparts to ferric scuts a green 
colour by deoxidation, and on boiling, deposits a blackish violot product 
soluble in alcohol. — 9. When the vapour is passed over lime at a low 
red heat, aniline and ammonia pass over, a large quantity of charcoal is 
separated, and chloride of calcium is formed; 

2C»NC1H« + 2CaO - C?«NH' + C» + 2Caa + NH» + «HO. 



CHL0RANIUN8« 289 

10. Mdted potasdum immened iq the vapoar of oblcHraQilipe^ forms 
ch]orid« aod ejaoide of potaesiQuiy with yirid incaqdesconce fuid ooparun' 
tion of a large quantity of charcoal. On the other h&ud, potamunp' 
fm^<mi with w^^f nduoea cmorapiline to aniline* (Ann, Fkarm. 
67, 79^) 

OcmJbmsAUmi, — Chloraniline ^ssolreB (qparinglj in 100^ ; the boiliag 
Bolntion becomes milky on cooling and deposits oetohedrons. 

It dissolyee readily in bisulphide of carb&n. 

Chloraniline is not so strong a base as aniline; it does not precipitate 
snlphate of alamina or the salts of ferric oxide, ferrous oziae or sine- 
oxide; it expels ammonia from aipmoniaeal-salts when heated wilJi them, 
but is itself predpitated by ammonia from its hydrochloric amd solution^ 
and neutralises acids but imperfectly. The SaUi of Chloranilme mostly 
crystaJlise readily^ and, in consequence of their sparing solubility, are 
generally precipitated on mixing an acid with alconolie diloraniline, ia 
the form of a crystalline pnlp^ which may be purified by irecrystallisation 
from boiling water or alcohol. They are mostly colourless or yellowish 
in mass, and yiolet when they contain excess of acid: they redden litmus 
eyen when complet^y saturated with the baae. Lixa the anilioe*salts, 
they impart a deep yellow colour to firwood and eldei^th, but widi 
chloride of lime, they assume only a yeiy fiunt yiolet tint, dianging after- 
wards to orange-yellow. They are immediately decomposed by alkalisj 
also by alkaline carbonates, with evolution of carbonic acid, inasmuch as 
that acid does not combine with chloraniline. 

Phogphate of (%^9At2w. r— Alcoholic chloraniline solidifies with 
aaueous phosphoric acid into a magma of crystalline laminiB, which dis- 
solye pretty readily in water and alcohol. 

StUphaie of OhloraniUne, ^^The white erystailtne magma^ into which 
alcoholic chloraniline solidifies when mixed with a small quantity of acid, 
yields, when diasolyed in boiling water, confused violet- white laminaB, and 
when dissolved in boiling alcohol, silyery needles arranged in stellate 
groups. The crystals w^n heated ffiye off a small quantity of chlo- 
ranilme^ then blacky and eyolye suljmuFons acid. They are less soluble 
in alcohol than in water. 

CryMtaU, Hofinann. 

12 C 72*0 40-82 

NCIO 67-4 32-55 

/S0» V 40-0 22-66 

(>lfGm«,HO,SO» 176-4 100-00 

ffy^^r^ddoraU of CMoranilijue. , — Hydrodiloric acid saturated at a 
boiling beat with chloraniline, yields on cooling lar^e crystals, which may 
be /itill farther developed by slow evaporation of tneir aqueous solution 
over oU of vitriol. They have the same form as hydrochlorate of bro- 
maniline <p. 278), aia=i 127'' 4S'. They contain 22-1 per cent of 
hydrochloric acid. They are permanent in the air, become opaque when 



284 BENZBNE: AZOCHLORINB-NUCLEUS C»NC1H^« 

lieatedy and sublime andecomposed when cautionslj heated, whereas 
sadden heating decomposes them, with formation of a violet yaponr. 

Nitrate of Chlorantline. — The solution of chloraniline in warm dilate 
nitric acid becomes filled, as it cools, with large crystalline laminsd, mostly 
of a reddish colour. These crystals, which cannot be sublimed without 
decomposition, melt when heated in a tube, into a dark-coloured mass^ 
which dissolves with splendid violet colour in alcohol, while part of the 
salt crystallises out undecomposed. The salt dissolves pretty readily in 
'Water and alcohol. 

A mixture of the aqueous solutions of chloraniline and protochloride 
of tin soon solidifies into a silver-shining crystalline mass. 

Aqueous mlphate of copper, which is not precipitated by aqueous 
chloraniline, soon becomes decolorised by boiling with crystalline chlo- 
raniline, and deposits a bronze-coloured crystalline mass, which is insoluble 
in water, and dissolves but sparingly in boiling alcohol, whence it 
crystallises in spangles on cooling. 

The cold aqueous mixture of chloraniline and eori'osive stibltmate 
immediately forms a white precipitate, but the hot mixture remains clear 
at first, but then quickly becomes turbid, and solidifies into a magma of 
needleHshaped crystals of the double salt. 

Aqueous chloraniline forms a red-brown precipitate with Urchloride 
of gML 

Chloraplatinate of Chloraniline. — A cold solution of hydrochlorate 
of chloraniline forms with bichloride of platinum, a beautiful orange- 
coloured precipitate, and a hot mixture solidifies on cooling into a magma 
composed of white crystalline laminso. These, when washed with a small 
quantity of water, and then dissolved in a larger quantity, are deposited, 
by evaporation over oil of vitriol, in crystalline nodules which redden 
litmus, uecome covered with a violet film on exposure to light, and dis- 
solve readily in water and alcohol, especially at a boiling heat. 

Hofmami. 

12 C 72*0 .... 21-58 22*03 

N 14-0 .... 4-20 

7 H 7-0 .... 210 2-30 

Pt 99-0 .... 29-68 29-34 

4 CI 141-6 .... 42-44 

C"NC1H«,HC1 + PtCl« .... 333-6 .... 100-00 

Aqueous chloraniline forms an orange-coloared precipitate with 
chloride of palladium, 

Chloraniline dissolves in wood-spirit, alcokol (readily when hot), in 
ether, (which abstracts it from the aqueous solution,) and in acetone. 

Oxalate of ChloranUine, — The solution of chloraniline in the warm 
aqueous acid yields on cooling, crystals, which when recrystallised from 
boiling water, form prisms made up of smaller ones joined together. 
They have a sweetish burning taste, and dissolve sparingly in water and 
alcohol; the aqueous solution becomes coloured on exposure to the air 
and deposits a red powder.— -It does not appear possible to obtain a bibaaic salt iii 
the crysUllsne state. 



TERCHLORANILINE* 285 

Crffgtali, Hofmann. 

16 C 96*0 .... 42-40 42-59 

NCI 49-4 .... 21-82 

9 H 9-0 .... 3-98 4-24 

9 72-0 .... 31-80 

CMNCiH«,HO,C<H>0» 226-4 .... lOO'OO 

The boi-satarated aqneons solution of cbloraniline mixed with tincture 
of gaUs, forms yellow flakes on cooling. — Chloraniline dissolves in oils, 
hoUiJixed and volatile. 



AzodOoniuMiudetu C»NC1*H>. 

Bichloraniline. 

(PNCPH' = C"NC1*H«,H«. 

Hofmann. (1845.) Ann. Pharm. 53, 88 and 57. 

By distilling bichlorisatine, still containing chlorisatinei with hjdrate 
of potash, long prisms are obtained consisting of bichloraniline with a 
little chloraniUne. (Hofmann.) 



AtoeUorinMiudeus C^Cl'H*. 



Terchloraniline. 

C"NCa»H* = C»NC1»H*,H». 

Erbmann. (1840.) J. pr. Cheni. 19; 331; 25, 472. 
Hofmann. Ann. Pharm. 53, 35. 

The Ckhrmdaimit of Erdmaim, who however OTerlooked the nitrogen contained in it. 

Preparation, 1. Distils over in the preparation of terchlorocarbolic 
acid (pp. 182, 3). — 2. In the action of chlorine npon aniline or chlor« 
aniline, there is formed a mixture of terchloraniline and terchlorocarbolic 
acid (pp. 250, 282); and when this mixture is distilled with potash-ley 
into a well-cooled receiver, the terchloraniline passes over in needles 
floating on the water, and an oil which solidifies in the crystalline 
form. 

Properties. Delicate, white, rery fragile needles and laminae, easily 
melting into a colonrless oil, which crystallises on cooling; has a pecu- 
liar odoor; yolatile. Neutral. (Erdmann, Hofmann. j 



286 BBMZKNE : AZOCHLOBOBBOM INB-NVCLBUS C>>NClBi«H>. 

Hofmaiin. Erdmamu 

It C 72*0 .... 86*70 37-65 .... 36*89 

N 140 .... 7*13 

8 CI 106*2 .... 5413 .... 53-58 

4H 4*0 .... 2*04 2*44 ..., 2*23 



C"NCPH« 196*2 .... 100*00 

JkcompotUionB. — 1. With nUrie acid it eyolvoe nitrons foineo and 
forms a yellow solution wbich turns red when mixed with potash. ^Erd- 
mann.) — 2. The vapour passed over heated soda-lime, yields a large 
quantity of ammonia, and when passed over melted potassium, it yields 
a large quantity of cyanide of potassium. (Hofoiann.) — Not decomposed 
hy distillation with potash-ley. (Erdmann, Hofmann.) 

ComUnatiofu. Dissolres spafitigly in cold, more freely in boiling 
water. (Hofmann.) 

Does not combine either with acids or with alkalis. 
Dissolves readily in alcohol and etkei\ (Hofmann.) 



AzocMorobromtne-nticleus (?*NClBr*H'. 

Chloroblbromftiiiliii^. 

C"NClBr»H* = C»NClBr*SSH*. 

Hofmann. (1 845.) Ann. Pharm. 53, 38. 

Preparation, 1 . Crystalliiie ohloiiUiiliBe ideated with anhydrous bromine 
becomes very hot and gives off a large quantity of hydrobromio acid, 
assumes a violet colour, and is converted, after it no longer absorbs 
bromine even when melted, into ohlorobibl'omaniline, which solidilSes on 
cooling, and must be washed with cold water and recrystallised from 
alcohol. — 2. When the whitish precipitate which bromine-water forms 
in an aqueous solution of a salt of chloraniline, is dissolved in hot alcohol, 
a pale violet solution is obtained which yields needle-shaped crystals. 

Properties. White prisms, often with a tinea of red. They melt in 
hot water, forming a orown oil^ which volatuises with the vapour of 
boiling water and sublimes in shining needles. 



12 C 


74-0 


.... 25*23 ... 
.... 4*91 
.... 12*40 
.... 56*06 
.... 1*40 ... 


Hoftntttm. 
25*43 

1*52 


N 

CI 

Z DE .•••*•. ••i.it.Mi... I 

4 H 


14*0 

*.M..«. 35*4 

160*0 

4*0 








CWNClBiaa* 


285*4 


.... 100*00 





It is decompoeed by strong nitric acid. 
It is insoluble in water. 



mrkonAi^tUM. 887 

li does not exhibit tbe eliatftcters of ft sidififtble bdsej diteolveft Indeed^ 
with Tiolet coloar, ill oU of vitriol, but is pfreoipitated thdreftoib by water; 
dissolves also in hot strong hydroMork addi but the gfeate^ part of it 
separates on cooling, and the rest oii addition of water. 

It dissolves without alteration in Wiirtn afnmtmia atid paUuh. 

Does not form oomponnds with ohloride of mercnvy or bichloride of 
platinum. 

Dissolves in ul6ohol and ttheTi (Hofmatin.) 



Nitrosaniline. 

C»»N*fi«0^ = C»N(l!IO*)H^,tf. 

A. H. Church & W. H. Pbbkin. Chenu Soc. Qu. J. 9^ 1. 

Formation and Pn^tpanxtion, By the action of nascent hydrogen on 
binitrobenzene : 

C»N^HKI* 4* iH te C»lf%«0^ 4 6H0. 

Pore zine in tbe form of a long strip is introduced into a cold saturated 
dlcoholic Solution of binitrobeiizeiie, ahd strong hydirochlorid acid added 
drop by drop^ whereupon the liquid in contact with the zino imtdediately 
acquires a fine crimson colouh Thd ai^tioii mtist be continu6d till the 
coloured liquid no longer forms a cloud when mixed with water^ the zinc 
being withdrawn whenever the liquid becomes too hot or the action too 
violent. When the actloh is coiiiplete. the zinc is completely withdrawn; 
the liquid neutralised with an alkali, the precipitate of oxide of zinc 
washed on a filter with strorig alcohol; the alcoholic filtrate with 
the washing evapoirated over the water-bath; and the residue further 
purified by washing with water^ then redissolved in alcohol and again 
evaporated. 

Properties Black shining^ brittle erusti easilv remoted from the 
eontaining vetoeL Its alcoholic solution is perfeotlT transparent to 
transmitted l^ht^ but by reflected IS^ht it appears absolutely opaque and 
of a fine orange-ted colour^ as if it held vermilion in suspension. — 
This phenomenon is well aeea bj the flame of aloohol letarated with a bafjte-Balt^ or 
better bf the tolv speetram, the red rif producinc no effect 

Char^ H PerkiB. 

liC » n "" W-Ol 6904 

2 N 28 .... 22-95 22*80 

6 H 6 .... 4-92 4-68 

2 O 16 .... 1312 13-48 • 

CttN«H«0» 122 .... lOCOO 10000 

NitrtManiline cannot be volatilised without decomposition: at a higher 
temperature, it becomes carbonised and gives off a wiiite yapoor. Heated 



288 BBNZBNB: AZONITRO-NUCLEUS (P^NXH^. 

witb soda-lime, it gires off all its nitrogen in the fonn of ammonia and 
aniline. It is decolorised by the prolonged action of nascent hydrogen. 
Nitrosaniline is nearly insoluble in water, but dissolyes readily m acids. 
With dilate salphario and nitric acids, it forms solutions of a deep 
crimson colour; boiling nitric acid dissolyes it with yellow colour; and 
fuming sulphuric acid, with an intense brown colour, which nearly disap- 
pears on addition of water. It likewise dissolyes, with splendid crimson 
colour, in highly concentrated hydrochloric acid, and the solution gradually 
deposits the colouring matter in the form of a reddish film haying the 
brilliant metallic lustre of copper. The same solution exposed to the air 
forms after a while a gummy mass, while a portion of the nitrosaniline 
separates. Alkalis precipitate nitrosaniline firom its acid solutions in 
brownish-yellow flakes, but if the action of the alkali be not long 
continued, the original crimson colour reappears on the addition of 
an acid. 

Nitrosaniline dissolyes readily in alcohoL IT. 



Az<mUr(Hiucleus (PNXH^ 

Nitraniline. 

(PN*HH)* = C»NXH*H«. 

HoFMAiYN & MuspRATT. (1846.) Ann. Pharm. 57> 201; also Phil. 

Mag. J. 29, 312. 
E. Arppb. Ann. Pharm. 90, 147; 98, 157. 

PrgMration. 1. Modification a. — The Paraniiraniime of Arppe.— 
The aqueous solution of binitrobenzene (p. 204) is saturated with ammo- 
niacal gas; sulphuretted hydrogen passed through the blood-red liquid, till 
the liquid is saturated with it and only a slight deposition of sulphur 
takes place; and the solution then mixed with hydrochloric acid and 
eyaporated, whereupon an additional quantity of sulphur separates, toge- 
ther with nndecomposed binitrobenzene. The filtrate is then mixed with 
potash, which precipitates a brown adhesiye resin; this resin freed from 
potash, by washing with cold water, and then dissolyed in boiling water; 
the orange-yellow solution filtered to separate a small quantity of undis- 
solyed brown resin; and the needles of nitraniline which separate on 
cooling, purified by recrystallisation from hot water. (Hofinann & Mus« 
pratt) Arppe further purifies the crystals with animal charcoal. 

Modification p. — Nitraniline of Arppe. — Pyrotartonitranil (C»N»H>*0*) 
is dissolyed in a boiline dilute solution of carbonate of soda, mixed with 
a little caustic soda, whereby it is conyerted, by taking up 2 At water, 
into pyrotartonitranilic acid, and the solution boiled till it no longer 
giyes a precipitate of pyrotartonitranilic acid on addition of nitric acid. 
The pyrotartonitranilic acid is then resolyed into nitraniline /3, and pyro- 
tartaric acid : 

C«N«H"OW - C"N«H«0* + CWH«0«. 

The yellow solution yields on cooling an abundant crop of yellow rhombic 
tables, which must be collected on a filter, washed with cold water, and 
purified by recrystallisation. (Arppe.) 



NITRANILINK. 289 

Properties, a. Needles of a fine yellow colour and an inch long; 
heavier than water. Thej melt at about 110° (at 108°, according to 
Arppe), forming an oil of a deep yellow colour, which boils at 285°, 
passes over in yellow vapours, and solidifies in the receiver, forming a 
laminated mass; at 100°, the crystals sublime in beautiful laminae, without 
previous fusion. (Hofmann & Muspratt) — IT. The sublimed crystals are 
rhombic tables of 51° and 129°, having one of the acute angles either 
perpendicularly truncated or bevelled with two faces, while the two 
obtuse angles are sometimes obliquely truncated, sometimes unaltered; 
macles are often formed with deep re-entering angles. Similar modifica- 
tions are exhibited by the crystals obtained from solution in water or 
alcohol. (Arppe.) ^. — The crystals are inodorous at ordinary tempera- 
tures, but when slightly warmed, they emit an aromatic odour having a 
distant resemblance to that of aniline; they have a burning sweet taste. 
They are perfectly neutral, and colour fir wood (as well as the cuticle) 
deep yellow, like aniline, but do not produce any olae colour with chloride 
of lime. (Hofmann & Muspratt.) 

%. p. Crystallises from the aqueous solution by slow cooling in long 
needles; but by more rapid cooling, in small tabular or needle-shaped 
crystals with angles of 69° and 11 1°, having the smaller angle truncated 
in such a manner as to produce a six-sided table with angles of 111^ and 
1 38°. From an alcoholic solution, the rhombic tables separate unaltered 
together with the six-sided tables; an ethereal solution yields sometimes 
tables, sometimes capillary needles; from an aqueous solution containing 
carbonate of soda, rhombic tables of 56° and 125° are obtained; by sub- 
limation; sometimes needles, sometimes irregular laminsB. The crystals 
melt at 141°, volatilise at about the same temperature, and sublime 
very beautifully when heated between two watch-dasses. At 100°, the 
sublimation is scarcely perceptible. The crystals /9 nave also scarcely any 
taste. (Arppe.) 











Hofmann & 
MoBpratt. 


Arppe. 


^ 










a. 


a. 




p. 


12 C 


72 


• ••• 


52-17 


.... o2*Zd .... 


52-01 


•••• 


52*03 


2N 


28 


•«•• 


20*29 


.... 20-52 








6H 


6 


• •• « 


4*35 


.... 4 04 •»•• 


4-37 


•••• 


4-40 


4 


32 
138 




2319 
100-00 


.... 22-69 








C^^N'HH)*.. 


.... 100*00 









DecompatUions, I. The vapour of nitraniline bums with a bright 
sooty flame. — 2. Nitraniline o distils when heated almost without 
residue; p leaves a very considerable quantity of carbonaceous matter. 
(Arppe.) — 3. Bromine converts nitraniline with great rise of tempera- 
ture and evolution of hydrobromic acid gas, into a brown resin whose 
solution in hot alcohol deposits yellowish neutral crystals, insoluble in 
water, acids, and alkalis, and probably consisting of nitrobromaniline 
C*'NXBr«H*. (Hofman & Muspratt.) — 4. liitric acid acts violently on 
nitraniline a, and converts it after long boiling into an acid which appears 
to be picric acid. (Hofmann & Muspratt.) — Nitraniline /3 is dissolved by 
nitric acid, oven in the highly concentrated state, without visible decom- 
position. (Arppe.) — 5. Gaseous chloride of cyanogen passed through 

TOL. XI. ^ 



SM BENZENE : AZONITRO*NUCLEUS C»NXH«. 

nielted nitraBiline oonverts part of it into binitromelanilinay while tbe 
greater portion ia eonvertod into a reeinons labstance. Aloobolio nitrani^ 
line is deeompoeed very slowly by chloride of cyanogen, and aqueous 
nitraniline in a peculiar manner; bat nitraniline dissolved in ether forms, 
with chloride of cyanogen, nothing bnt hydrochlorate of nitraniline, and 
yellowish needles of nitraniline-urea. (Hofmann and Muspratt.) 

2CJ«N«H«0* + 2H0 + C?Na - CWN»H»CM,Ha + C"N»H'0«. 

G, The solution of nitraniline in bromide of ethyl quickly deposits, even 
at ordinary temperatures, large pale yellow crystals of hydrobromate of 
ethylonitraniline (C»NXH",HBr). 

Coffibinations, Nitraniline dissolves very sparingly in cold, but 
somewhat copiously in hot tmtei', (Hofmann & Muspratt.) Nitraniline a 
dissolves in 600 pts. of water at 185°, much more readily in boiling 
water] p dissolves in 1250 pts. of water at 12*5 and in 45 pts, of boiling 
water. (Arppe.) 

Nitraniline is a very weak bsjse; it does not precipitate any metallic 
salt, and from its salts, some of which are crystallisable, it is precipitated 
in the crystalline form by aniline as well as by the caustic alkalis and 
alkaline carbonates 

Sulphate of a'NUraniline forms shining microscopic rhombic tables 
which have but little taste, and form a perfectly colourless solution in 
water, from which the base is precipitated in the cr3r6talline state by 
potash and ammonia. 

SfdphaU of ^Nitraniline, — A solution of /3-nitraniline in dilute sul- 
phuric acid deposits, after gentle evaporation, large shining laminaa of the 
sulphate; smaller crystals exhibit under the microscope the form of 
square tables. The salt has a strong sour taste, is decomposed by 
water, but \^ not altered by exposure to the air. The hi-add salt 
C"NH«0* + 2(H0,S0») contains 34-41 p.c. sulphuric acid. (Arppe.) 

Hydrochlorate of a-NitranUine. — The colourless solution of the base 
in hydrochloric acid, yields by evaporation, nacreous crystalfl^ extremely 
soluble in water and alcohol. (Hofmann & Muspratt) Elongated 
rhombic tables with angles of 120° and 60°, which are permanent in the 
air and dissolve readily in hydrochloric acid; they are decomposed by 
water, which separates the greater part of the base. (Arppe.) 

Bydroohlorate of fi-Nitraniline. — ^-nitraniline forms with boiling 
hydrochloric acid, a yellow solution, or if the acid is in great excess, a 
colourless solution, which, on cooling deposits rather large, colourless, 
tabular crystals, which in their simplest form, are four-sided tables, with 
angles either (a) of 95° and 85°, or (6) of %&'' and 115°; by the combination 
of these two forms, the acute angles of a being truncated by 6, six-sided 
tables are formed; and by the truncation of ^l the angles of a, eight- 
sided tables. The salt is easily decomposed, both by heat, which causes 
it to turn yellow and give o£P acid, and also by water which separates 
the base almost completely; alkalis precipitate the nitraniline in the 
crystalline form, bnt the precipitate rediesolves in excess of the alkali. 
(Arppe.) 



12 C , 

2 N 


NITRAKIUNB, 

Mugpratt(a). ^"TP^W- 

72-0 „^ 41-28 
28*0 .... 16*06 


1 H 


7*0 .... 4«01 


4 O 


B2'0 .... 18*35 


CI 


36-4 „„ 20-30 „., 80-87 .... 20-20 


CMN«H"CH,Ha... 


174-4 .... 10000 



Ml 



Nitrate of orNitramUne. — Crystalline powder, easily soluble in water, 
bat sparingly in nitric acid : hence when nitric acid is poured upon the 
base, a white crystalline powder is produced which disappears on addition 
($f water, (Arppe.) This result is not in accordance with Hofmann & Muspratt's 
statement that a-nitraniline is violently decomposed by nitric acid. 

Nitraie of ^Nitramline. — The base dissolves very readily in warm 
nitric acid. The salt crystallises in shining needles several lines long 
and perpendicularly truncated, and is decomposed by water. (Arppe.) 

CMoroplatinate of a-NiiranUine. — The alcoholic (but not the aqueous) 
solution of hydrochlorate of a-nitraniline forms with bichloride of 
platinum, a yellow crystalline precipitate, which must be washed with 
ether, dissolves readily in water and alcohol, and contains 28*62 p. c. 
platinum; therefore = C»NXH*,HCl,PtCl". (Hofmann & Muspratt.) 

Chloroplatinate of p-NUranUine. —a. C"NXH«,HCl,PtCP.— A con- 
centrated aqueous or alcoholic solution of bichloride of platinum, is 
mixed with a warm concentrated solution of hydrochlorate of /3-nitra- 
niline; the resulting yellow precipitate collected in an empty glass 
funnel; the mother-Uquor left to drain; and the precipitate washed, first 
with an alcoholic solution of /^nitraniline, and finally with ether. — Or, 
the two salts are mixed in the state of concentrated alcoholic solution; 
the precipitate rinsed with a small quantity of water; and the mother- 
liquor removed as completely as possible oy pressure. — The salt, when 
dry has a yellow colour. From a concentrated alcoholic solution, it crys- 
tallises almost instantly in capillary needles united in stellate groups. 
May be heated to 100 without decomposition, but at a higher tempe- 
rature, it takes fire and burns with slight detonation. Dissolves in water, 
and much more readily in alcohol; soluble also in ether : water added to 
the alcoholic solution throws down a copious precipitate of the unaltered 
salt The aqueous solution is decomposed by evaporation; the alcoholio 
Bolutioii is more stable. The solubility of the salt in water, alcohol, and 
ether, is increased by the presence of hydrochloric acid. The crystals 
gave by analysis 38'Q2p. c. platinum; the precipitate formed by water 
in the alcoholic solution, gave 38*45 p. c. (Arppe.) 

h. G>'NXH*,H01,2PtCl*. — Remains as a yellow less soluble eom- 
pound when the salt a is washed with a mixture of alcohol and ether. 
Contains 38*16 p. c. platinum. It is partially dissolved by alkalis, 
forming a red solution; but part remains undissolved in the form of a 
brick-red powder, which dissolves with red colour in water and in 
alcohol. The aqueous solution once yielded small regular ootohedrons of 
a >ed colour. (Arppe.) 

0»aiaU of »J^itramlme,-^An alcoholio solution of a-nitraniline forms 
with alcoholio oxalic acid, yellowish crystals, which, when washed with 
ether and dried on a tile, contain 41 '30 p. o. C an4 d'Od H| and are 



292 BENZENB: AZONITRO-NUCLBUS C«NXm«. 

therefore C"NXH*,HO,C*H-Ol (Hofniann & Mnspmit) — Osralate of 
p-Nitramline crystallises in delicate needles and laminso : it is an acid, 
sparingly soluble salt, and forms a yeUow solution. (Arppe.) 

Tartrate of a-NHraniline forms a yellow solution from whieH the salt 
crystallises in yellow rectangular tables. Potash decomposes the solution, 
separating the base in the form of a yellow crystalline precipitate soluble 
in excess of the alkali. — Tartrate <f p-NUraniline crystallises in yellow 
needles; potash does not precipitate^ but dissolves it, forming a red 
solution. (Arppe.) 

A solotion of either modification of hydrochlorate of nitraniline, mixed with a 
recently prepared infasion of galUnuU and afterwards with a small quantity of potasby 
3rields a copious flooculent or almost gummy precipitate, which is decomposed by ezcen 
of potash I a portion of the base being separated in the crystalline form. (Arppe.) 

Nitraniline dissolves with red-brown colour in alcohol and ether, 
(Hofinann k Muspratt). Both modifications dissolve with ^Mility in 
alcohol and ether. (Arppe.) 



ir. Jzonitro-nudeus C"NX*H». 

Binitraniline. 

Gottlieb. Ann. Pharm, 85, 17. 

Diniiraniline, Dinitrophenylamine, 

Formation and Preparation. By the action of alkalis on citraco- 
binitranil : 

C»N»H70» + 4H0 = CWN»H*0« + C^HH)^. 
ciCracobinitranil. biuitraniline. citraoonic add* 

When citracobinitranil is treated with a boiling dilute solution of 
carbonate of soda, carbonic acid is evolved^ and the light flooculent 
crystals of the anil are partly dissolved^ and partly converted into a 
heavy, yellow, crystalline powder consisting of biuitraniline; when the 
action is complete, this substance separates out in more definite crystals. 
If the boiling be not continued long enough to ensure the complete decomposition of 
the anil in the manner aboye-mentioned, the mother *liquor is found to contain citraco- 
binitranilate of soda as well as citraconate. The binitranilino is purified by 

crystallising; it several times from boiling water. 

Properties. Crystallises by spontaneous evaporation of its solution 
in a mixture of alcohol and ether, in greenish-yellow, rather brilliant 
tables, exhibiting a bluish tint by reflected light on the lateral faces. 
Inodorous. Boils at 185^ giving off yellow vapours, which condense in 
the form of a yellow sublimate; the melted portion solidifies on cooling 
into a deep yellow crystalline mass. 



AMIDONITRANILINB. 293 



12 C 


Crystals. 

72 


• .•• 0.7*0i ... 

.... ^^'"3 ... 
.... « /4 ... 
.... o4*!f7 ... 


Gottlieb. 
39-28 


3 N 


42 


23-28 


5 H * 


6 


2-80 


8 O 


64 


34-64 


CMN»H»0» 


183 


.... 100-00 ... 


100-00 



Heated suddenly in a tube, it blackens and explodes with facility. — 
Sulphide of ammonium conyerts it into amidonitraniline. 

CMN»H«08 + 6HS « C»2N»H70< + 4HO + 6S. 

Binitraniline dissolves »paringlj in cold water, but leadily in boiling 
water and in hot alcohol. 

It does not combina with acids. (Gottlieb.) %. 



Azotamidogen-niideuB C"NAdH*. 

Semibenzidam. 

C»N»H* ? = C"NAdH*,H». \ 

ZiNiN. (1844.) J. pr. Chem. 33, 34. 
Azophenylamine (Gerhardt), Azaniline, 

When an alcoholic solution of binitrobenzene (p. 205), is distilled 
with hydrosulphate of ammonia, there remains, together with a large 
quantity of precipitated sulphur, a yellowish-brown resinous substance, 
which is insoluble in water, and separates from boiling alcohol or ether, 
when left to cool without contact of air, in yellowish flakes. 

These flakes contain 8 At. H to 12 At. C; they melt under boiling 
water into a brown viscid liquid; when exposed to the air, especially in 
the moist state, they quickly assume a greenish colour; and the yellow 
solution in alcohol or ether quickly becomes darker on exposure to the 
air, and deposits a greenish powder. 

The compounds of this substance with sulphuric and hydrochloric 
acid are yellow, easily deoomposible salts, nearly insoluble in water, 
alcohol and ether. (Zinin.) 



IT. Azonib'oamidogen'nudeui C"NXAdH*, 

Amidonitraniline. 

C"N»H'0* = C«NXAdH»,H«. 
Gottlieb. Ann, Pharm. 85, 27. 

Axophenylamine (Gottlieb), Nitraxophenylamine (Gerhardt). 



294 BENZENE: AZONITftOAMIDOGEN-'KUCLEUS CONXAdH*. 

Preparation By the action of snlpbide of ammoniam on binitraniline 
(p. 293). When this substance is boiled for about two hours with a large 
excess of solution of sulphide of ammonium; the liquid acquires a dark 
red colour, the crystals of binitraniline disappear, and are succeeded by 
a network of delicate shining dark red needles of amidonitraniline, which 
gradually increase in quantity and are likewise abundantly deposited after 
the action is completed and the liquid has cooled* The compound is obtained 
in the purest state by precipitating it from the hydrochlorate or oxalate 
purified by several crystallisationsi and then reorystallising it two or three 
times from hot alcohol. 

Properties. Ciystallisefl in long slender needles united in groups, 
haying a slight red colour when dry, and exhibiting a golden irideeoenoe 
on their broader faces. When separated by ammonia from a saturated 
solution of one of its salts, it takes the form of a dull brick-red powder; 
but dilute solutions deposit it in small, reddish yellow, shining plates. 
Melts at a high temperature and volatilises in great part without 
decomposition, forming a woolly sublimate. When suddenly heated, it 
explodes slightly, leaying a residue of charcoal. 



12 C 78 ;... 4t*0S 1...U.. 46-86 

3 N 42 .... 27-45 27*69 

7 H 7 .... 4-57 4-55 

4 O 32 .... 20«92 tO-dO 

C"N«H70< 153 .... 100-00 lOO'OO 

CombiruUiona. Amidonitraniline dissoWes readily in ivater, forming a 
deep red solution. 

It combines with acid$, forming salts which are deoompoeed by water 
and by alcohol, with separation of the base : hence in preparing them, it 
is necessary to let them crystallise in presence of an excess of acid. 

Sulphate of AmidonUraniline, C«N*H'0*,HO,SO* is obtained by dis- 
solving the base in warm dilute sulphuric acid, and separates on cooling 
in yellowish scales, having a fatty lustre and containing 8*20 p. c« 
sulphur. 

A mixture of the solution of this salt with idlpkftte of alumina, do«s not yidd aay 
double salt when left to •▼aporate. 

jBydrochiorate of Amidonitraniline. -— May be prepared by boiling the 
crude base with dilute hydrochloric acid, which dissolves it, leaving only 
a residue of sulphur and a secondary product of a dull groen crystalline 
aspect, part of which also passes into the solution. To free the salt 
completely from this impurity, it must be repeatedly dissolved in boiling 
dilute hydrochloric acid and reciystallised. -^ From a concentrated acid 
solution, it separates in yellowish -brown needles; from a dilute solution 
by spontaneous evaporation, in oblique prisms often 4 or 5 millimetres 
in length and united in groups. These crystals exhibit a light brownish- 
green colour by transmitted light, and a peculiar blue iridescence on some 
of their faces by repeated light. The acid solution has a greenish -brown 
colour. The crystals contain 2 At. water which they give off at 100^ or 
in vacuo or over oil of vitriol at ordinary temperatures. At 100^, however 
partial decomposition takes place and nydrochlorio acid is given off. 



AHIPONITRAMILINB. i95 



12 G .>. 

3 ri ..« 


..i...«u«, 72-0 ..» 88-00 ... 

M.......M...I.*. 42-0 .*.! 22-16 


Gottlieb. 
37-78 


8 H ... 


4 8-0 .... 4-22 ... 


4-24 


CI ... 

4 O ... 


35-4 .... 18-73 ... 

32-0 .... 16-89 


1917 



C«N»H'0<,HC1 189-4 .... 10000 

The ci^BtaLi contain 17*08 p. c. chlorine^ and are thereforo 
C»N»H'0*,HC1 + 2 Aq. 

Nitrate of AmidonitranUine, — Wann dilate nitric acid readily 
dissolves amidonitraniline, but the eolation soon acqaires a dark colour 
and deposits flakes indicating partial decomposition. The pure salt may 
howerer be obtained by moistening the base with water^ and pouring 
dilute nitric acid upon it by small portions : it it then immediately con-* 
verted into a thick magma of micaceous scales^ which may be freed from 
the mother-liquor by pressure between paper. The salt thus prepared 
is anhydrous^ and may be kept for months over oil of vitriol without 
losing its lustre. 

.Gottlieb. 

12 C 72 .... 33-33 33-78 

4 N i 56 .... 25-93 2607 

8H 8 .... 3-70 3-87 

10 80 .... 37-04 36-28 

- ' - — 

C»N»H70^H0.N0« 216 .... 10000 100-00 

A tolation of hydrocfalorate of amidonitraniline mixed with bichloride of platinum, 
does not yield a doable salt, the platinam being rapidly reduced to the metallic state. 

PlaiinhydrocyaruUe of Jmidonitranilinei 2(CNSH70<,HCy,PtCy) -t- 5Aq. 
— Obtained by adding crystallised hydroohlorate of amidonitraniline to a 
boiling aqueous solution of platinocyanide of magnesium. Mii, 53). 
The solution separated by filtration from a small quantity of dark inso- 
luble matter, gradually deposits a mixture of the platmhydrooyanate 
and the free base, which latter may be removed by digestion with a small 
quantity of dilate hydrochloric acid. — Large Jaminsd, having a light 
brownish-yellow colour and strong lustre, and giving off their water at 
tl8^. They cannot be recrystallised from water without partial decom- 
position. 

At 112«. OoltUflb. 

16 C 96 .... 81-48 ai-74 

5 N ,. 70 .... 22-96 2312 

8 H 8 ...4 2-62 2-76 

Pt 99 .... 32-46 32-28 

4 O 32 .... 10-49 10-10 



-....—...- - . - . - - ,^ 



C"N»HW,HCy>PtCy .... 308 .... lOOOO 100-00 

The compound dried over oil of titriol learee when ignit^ SO* 15 p. o. 
platinum, whence it is 2(C»N'HW,HCy,PtOy) + SAq. 



296 BENZENE : CONJUGATED COMPOUNDS OF ONE AT. C^VLK 

Oxalate of AmidonitranUne. — Obtained by disBolving the base in 
aqueous oxalic acid. From concentrated solutions it separates in jellow 
needles; from more dilute solutions, in brownish-yellow prisms, exhibiting 
a bluish iridescence on certain faces. It is anhydrous, and dissolves bnt 
sparingly in cold water. 



28 C .... 
6 N 




... 168 

... 84 


.... 42-43 .. 

.... £x £1 ... 

404 .. 
.... 32-32 .. 


Gottlieb. 

42-83 

21-41 


16 U •••■ 




.... 16 


4-20 


16 O 




... 128 


31-56 


2C"N»H; 


ro< Cm^Os .... 


.... 396 


.... 100-00 .. 


10000 



Amidonitraniline dissolyes in dechol and ether^ forming deep red 
solutions. (Gottlieb.) IT. 



Ckmjugaied Compound* of 1 At, C^NH* or a similar Nucleus, 

Sulphanilic Acid. 

Gbbhardt. N, J. Pharm. 10, 5; abstr. Compt rend, 21, 285. 

AnilinickuftfeltUure, Sulfanilinsdure, Acide sulfaniUque, Pkenylsnlphamic acid. 

Formation, By heating oil of vitriol with aniline, formanilidc, 
oxanilide (Gerhardt), carbanilide or aniline-urea (Hofmann), or by 
boiling sulphobenzolic acid with nitric acid, and treating the resulting 
nitrosulphobenzolic acid, C"XH',2S0' with sulphuretted hydrogen, after 
combining it with ammonia; it is thereby converted into sulphanilate of 
ammonia. (Laurent, Compt, rend, 31, 538.) 

Preparation, 1. A solution of aniline in a slight excess of sulphuric 
acid is evaporated to dryness; the residue heated, cautiously and with 
constant stirring, as long as water and aniline continue to escape, and 
crystallised from boiling water. — 2. Better : the mixture of formanilide 
and oxanilide which remains after heating oxalate of aniline to 1 80°, is 
mixed with oil of vitriol to the consistence of a thick pulp ; this mixture 
heated in a flask, but so gently that no blackening shall take place, and 
as long as carbonic acid and carbonic oxide continue to escape with effer- 
vescence; the residue exposed in a shallow dish to a moist atmosphere; 
the crystalline mass suspended in and washed with cold water, and 
recrvstallised from boiling water. (Gerhardt.^ — 3. The solution of 
anilme-urea in oil of vitriol is gently heated; tne brownish mixture of 
sulphate of ammonia and sulphanilic acid, which forms, with evolution 
of carbonic acid, washed with water; and the crystalline mass thus pro- 
duced, washed with animal charcoal and crystallised from hot water. 
(Hofmann, Ann, Pharm, 70, 133.) 



SULPHANILIC ACID. 297 

Properties. Colonrless, rhombic tables, having a strong lustre and a 
yeij sour taste. 

Crytialt, Gerhardt; Hofmaxm. 

12 C 72 .... 41-62 41-95 

N 14 .... 8-09 8-60 

7H 7 .... 4-05 4-33 

2 8 32 .... 18-49 18*90 .... 18-75 

6 48 .... 27-75 

CBNH',2S0» 173 .... 100-00 

Deeompmtione. 1. The acid, when subjected to dry distillation, 
becomes carbonised, melts, and gives off a large quantity of sul- 
phurous acid, together with an oil which solidifies on cooling, and 
forms with water, sulphite of aniline.—- 2. The aqueous solution of 
sulphanilic acid mixed with cA^ortnf-water, assumes a pale carmine- 
colour, gradually changing to brown-red. — 8. The same solution, even 
when very dilute, becomes milky on addition of 6romtn^water, and 
yields after a while, a white curdy precipitate insoluble in potash.-^ 
4. The solution is coloured brown-red by cAromtc Of ie?. — 5. Gold concen- 
trated nitric acid does not act upon sulphanilic acid; but hot nitric acid, 
forms, with great evolution of gas, a red solution which deposits a resin 
when left at rest. — 6. Anhydrous sulphuric acid carbonises the greater 
part of sulphanilic acid, in spite of external cooling. — 7. When the acid 
is heated with potash^lime, pure aniline distils over, and a sulphate is left 

behind. In the case of other anilidea also, the nitrogen cannot be determined 
(according to Will & Yarrentrapp't method) by means of potash-lime. (Grerhardt.) 

ComhifuUions, The acid dissolves sparingly in cold, more abundantly 
in boiliuff tifater. (Gerhardt.) 

Sulphanilates. The acid decomposes alkaline carbonates with effer- 
vescence; it neutralises bases perfectly, and is separated by mineral acids 
from the concentrated solutions of its salts, in slender needles. 
(Gerhardt.) 

StUphanilate of Ammonia. — - The solution of the acid in aqueous 
ammonia yields by spontaneous evaporation, highly lustrous, thin, six- 
sided or rectangular tables, which become dull at 100**, and at a higher 
temperature, yield sulphurous acid and the same oil as the free acid. 
(Gerhardt.) 



(yyitak at 100^ 




Gerhardt 


12 C 72 


.... vS'ou .. 


37-6 


2N 28 


.... 14-74 




10 H 10 


5-26 .. 


6-4 


2 S0» 80 


.... 42-11 




C>3NH«(NH<),2SO» 190 


.... 10000 





StUpharUlate of Soda. — The aqueonsjacid neutralised^wiih carbonate 
of soda, crystallises by spontaneous evaporation in large eight-sided 
tables, whereas from boiling alcohol (which leaves a small quantity of 
carbonate of soda mixed with the salt) needles are obtained. The 
tabular crystals contain 14*65 p. o. (4 At.) water; when hefttod, they give 



298 BENzBNB ; C0NJUa4Tn COMPOUNDS OF ONE AT. C»NH>. 

off tiM wnfter whkk hmmk and itttmneseonee; then ttuu brownj erolre 
stinking Tapoafs together with a brown oil containing aniline; wad, 
when heated in the air, yield a bine flame aod snlphurous acid. On one 
oocasioui large prisms were obtained, containing 5d'6 p. c. (24 At.) 
water of crystallisation. (Gerhardt) 



12 C 


Dried at 100*. 
72-0 


.... 36-88 .. 
.... 7-17 
.... 308 .. 
.... 11-89 .. 
.... 16-39 . 
... 24-59 


Oeriiardt 
36-9 


N 

6 H 




.... 14-0 
6-0 


...... 3-2 


Na 

2 S 


••••*•••••■••■•••« 


.... 23-2 
32*0 


11-4 

17*0 


a o ...* 




48-0 












C»mB«(Nl 


J<),280» ... 


195*2 


.... 10000 





SulphanOate of Baryta. C^'NH'Ba»2SO'.^Beotangnlar prisms, some* 
what freely soluble in water (Gerhardt)« containing 38'40 p. «• bariam* 
(Bnckton & Hofmann.) 

iStdphanUcUe of Oopper. — Protoxide of copper dissolves very slowly, 
bat the hydrate, readily, in the* aqueous acid, forming a green liquid, 
which, by eraporAtion and cooling, yields short, hard, blackish-green 
prisms having a strong lustra. These crystals, when heated above lOO^^ 
give off their water and assume a dingy yellow colour^ aud at a higher 
temperature swell up in vermiform masses. 



12 C ... 

N 
10 U 

Cti 

2S... 

10 o... 



CfryttaU* 



••I 







Gerbardt* 


72 


.... 30'00 ... 


80-5 


14 


.... 5-84 




10 


4-17 


«*.4. 4 m 


32 


•••• lo do ••« 


..... 13*0 


32 


.... 13*33 




80 


.1.* 33*33 





C»N«Cu,2S0< + 4Aq »... 240 .... lOOOO 

SulphanilaU of SUtfer. O^^If^Ag,iSG^.— Shinmg scales (Gerhardt), 
containing, when dried at 120°| 38*58 p« o. silver. (Backton 8c Hofmann.) 

Sulphanilate qf Aniline, — Aqueous aniline^ saturated while hot with 
sulphanilic aoid» yields on ooolii^i needles oonsisting of the lEree aoid^ 
and afterwards on evaporating the mother-liquor, laminie of the aniline* 
salt. 

Sulphanilic acid dissolves in alcohol less easily than in water. 
(Gerhardt) 



^. Bisulphanilic Acid. 

C»NffS*0" = C"NH^4S0«. 
O. B. BucKTOK & A. W. Ho^MAKir. Chem. Soc Qu. J. 9, 259. 



BlStfLraAmUC ASW* 399 

Obtained by thd aottoil 6f ftimlii^ ftblphttrid UmiA Ofi solfyhftnills Acid* 
Dry and finely pulrefiaed sttlphanilid amd is stirred up with ftttniug 
Bttlpbaria aoid to ths eoftsistenoe of a thin paste} the mixture heated in 
an lUr-batb to between 100° attd 170*'j at whieh teinpemture sulphttTous 
acid just begins to escape; and tlie digestion continu^ for abottt seten 
hours^ or tul a portion taken out on a glass f dd no longer Solidities on 
cooling. The mass, which has the consistence of treacle, is then 
dissolved in cold water, and separated by filtration from a black insoluble, 
apparently crystalline substance. 

Bisulphanilic acid separated from the leadnBalt by sulphuretted 
hydrogen has a very acid and pungent taste; it crystallises with great 
difiiculty, but is precipitated m white grains from a strong aqueous 
solution by addition of alcohol; the precipitation is {Militated by adding 
a little ether. 

12 C _ 72 28-46 

N 14 5-53 

7H 7 2-76 

4 B 64 26-30 

IS O I. 96— 87-95 

C"NH',480» 253 10000 

May abo be regarded as C^H*Ad,4S0*. 

Bisttlphanili<$ acid is easily soluble in toater. 

The BisuiphanUatei contain 0^'NH<^M>,4S0^ The barium and silver • 
salts are soluble In Water, but insoluble in alcohol and ether. 

BistHphanilate of baryta, «— The aqueous acid obtained as above, is 
saturated with carbonate of baryta, the liquid evaporated to drytiess, 
whereby a further separation of the black substance Is effected, the 
baryta-salt redissolved, the solution treated with a small quantity of 
alcohol, which precipitates a small quantity of sttlphanilate of baryta, 
and the filtrate evaporated either over the water-bath, whereby a horny 
fissured mass, is left^ or in vacuo, whereby the salt is obtained in 
microscopic crystab. 

Backton & Hofmann. 

12 C 72-0 .... 18-58 

N 14-0 .... 3-60 

5H 50 .... 1-28 

2Ba 137-2 .... 8530 35-30 

4 8 ......4 .4.U.4 64*0 «..« 16-49 imt... 16*32 

12 O V 96*0 .... 24-75 



C"NH*Ba^,4S0* ..u.... 388-8 .... 100*00 

The salt heated on platinum foil, blackens without inflaniln^. Heated 
in close vessels, it yields a vapour which sublimes in beautiful crystals, 
probably of sulphite of aniline. It is decomposed by strong nitric acid, 
yielding sulphate of baryta, and a yellow liquid, which when evaporated, 
leaves crystals having a verf bitter taste. 

BistUphanilate (/ Silver. 0»*NH*Ag»,4S0». — By saturating the 
aqueous aeid with carbonate of silver, and precipitating with a mixture 



300 BENZBNB : CONJUGATED COMPOUNDS OF ONE AT. C»NH*. 

of alcohol and etber, the salt h preoipitated in colourless cijstalline 
grannies; the precipitation is accelerated hy stiznng. Bj spontaneons 
evaporation, the salt is obtained in small tiu>nlar dystals which blacken 
when boiled with water. They contain 45*53 per cent, of silver. 
(Bnckton & Hofmann.^ 

Bisnlphanilio acid ib insolnble it alcohol and ether. % 



Methaniline. 

C"NH* = C»(C»H»)NH*,H». 

A. W. HoFMANN. (1850.) Ann. Fkarm. 74, 150. 

Metkyleniline, MMylophenylamine, Fomumiline, 

Prevaratum. The mixtore of aniline or excess of iodide (or bromido) 
of metnj], which must be made eradually to prevent too great a riee of 
temperature, yields crystals of hydriodate (or hydrobromate) of methani- 
line, from the aqneons solution of which salts, the oily base may be 
separated by potash. 

FrapertieB. Transparent oil, which boils at 192°, has a peculiar odour, 
and colours aqueous chloride of lime violet, but not so strongly as 
aniline. 

The salts of methaniline are sparingly soluble in water, and are sepa* 
rated from their aqueous solution in the crystalline state by acids. 

The MoroplatinaU is precipitated in the form of a limpid oil, quickly 
changing to pide yellow crystalline scales which must be quickly washed 
with cold water and dried. They soon turn black from decomposition^ 
and when alcoholic solutions are used, a black mass is immediately preci- 
pitated. The crystals contain 31 '55 p. c. platinum, and are therefore 
C"NH*,HCl,PtCK 

The oxalate crystallises readily, but quickly decomposes, reproducing 
aniline. (Hofmann.) 



Fonnanilide. 

C"NH'0» = C»(C*H)AdH*,0». ? 

Gbbhardt. (1845.) N. Ann. Chim, Phys. 14, 120 and 15, 88; also 
JV. J. Pharm. 8, 58; also J. pr. Chem, 35, 295. — i^. J. Pharm. 
9, 409* 

Formation (p. 262). ^2 

Preparation. The mixture of formanilide and oxanilide obtained by 
heating oxalate of aniline to between 160° and 180°, is treated with cold 
alcohol to extract the former; the solution partially evaporated and 



eaa 



ANILOCTANIG ACID. 301 

separated from a brown prodnct formed from the oxalate of aDiline hj 
the action of the air; and the formanilide obtained by farther evapora- 
tion, first in colourless oily drops which sink to the bottom, and after- 
wards by evaporation in prisms. 

PropeHies,^ Flat, acuminated, rectangular prisnjb resembling nrea; 
melts at 46^, into an oil which gives off vapours even at 100°, remains 
liouid much below 46^ but if then stirred with a glass rod, instantly 
solidifies. Slightly bitter, neutral. 

4fter/u$ion at 100^ Gerhardt. 

14 C 84 .... 69-42 6915 

N 14 .... 11-57 

7 H 7 .... 5-79 6-10 

2 O 16 .... 13-22 



C"NH70» 121 .... 10000 

Metameric with benxamide. 

Deoompodtions, 1. With hot oil of vitriol, formanilide forms sulpha- 
nilio acid, without blackening, but with evolution of carbonic oxide. 

C"NIFO» + 2S0» - 2CO + C"NH7,2SO«. 

Dilate sulphuric acid heated with formanilide eliminates formic acid. — 
3. Dilute chromic acid mixed with formanilide turns green after a while, 
but when the mixture is boiled, with addition of sulphuric acid, a preci- 
pitate is quickly formed of the same nature as with aniline. — 4. Cold 
potash-ley does not act upon it, but boiling potash eliminates aniline in 
a few seconds. 

CombinoHons, Aniline dissolves with tolerable facility in water, espe- 
cially in hot water. It melts under water even below 46°, and remams 
liquid for several days after cooling. (Gerhardt.) 



Anilocyanic Acid. 

C"NH»0« = C»*CyH,0«, 
A. W. HoFMANK. (1850.) Ann, Fharm. 74, 9. 

Formation. By the dry distillation of melanoximide, sparingly by that 
of oxalate of melaniline. Not by distilliag snlphocarbolate of baryta with cyanate 
of potash, or by distilUiig anthranilic acid or salicylamide with phosphoric acid. 

Preparation, Well dried melanoximide is subjected to dry distilla- 
tion in perfectly dry vessels; and the pale yellow distillate cooled, 
filtered to separate it from the crystallised carbanilide, and rectified in a 
tube, moisture being carefully excluded throughout the whole setiea of 
operations. 



308 BENZENB : COKJUQATCD COlfPOUHDS 07 ONE AT. 0»KH«. 

Piy^pertm. -w Thin, tmnspwenly nolonrlofli, BiroBgly lefraotliif liquid^ 
heftyier than water, boiling at ITS'" and finally at 180^ haTUig an 
extremely pow^ul odonr of eyanegen, hydrooyanie Mid and aniline 
together, exciting a copious flow of tears, uid prodooing fuffooation in 
the throat when inhaled. 



14 V4 #r«*Mr«*«M|t« 

N 

5 H 


IffM'tM •'4 

14 

5 


.„. 70*58 
.... 11-77 
.... 4-20 
.... 13-45 


RofiBavn* 

70-02 

11-92 

4-37 


2 O 


16 


13-69 








CMNH»0« 


119 


.... 100-00 


100-00 



« C»NH> (cyuiic add) -¥ C^H^ (Hofinaim.) 

Deeampoiiiumi. 1. With oil of vitriol, the acid is resolyed into carbonic 
oxide and snlphanilic acid : 

[C"NH»0» + 2S0» - 2CO + C"NH»,280».] 

2. With hydrocUoriQ add, \i is resolyed into oarbonic acid and hydro- 
chlorate of aniline : 

C"NHW + 2HO + HCl - 2C0« <■ (?*Nir,HCl. 

3. With water, into carbonic acid and crystallising carbanilide; 

aCi«NH»0« + 2HO - 2CO> + C^WfliaO*. 

4. With poUuk-Uy^ it is qoiokly resolyed into carbonate of potash and 
free aniline ; 

C><NH«0» + 2H0 + 2KO - 2(KO,C02) + C^NIF. 

5. With ammonia, it eyolyes great heat, and immediately solidifies in the 
form of aniline^urea : 

C. With aniline it becomes heated, and immediately solidifies in the form 
of carbanilide : 

C"NH»0» + C»NH7 = C«N«H»OS. 

7. Its clear solution in toood-spirU, alcohol, fiueUoil, or carMic acid, the 
formation of which is attended with great eyolntion of heat, quickly 
deposits beautiful crystals, which melt at 100°, are insoluble in water, but 
dissolye readily in alcohol or ether. These crystals appear to be mix- 
tures. Those obtained from wood-spirit contain 63*40 p. c. C and 7'3S H, 
and are therefore perhaps C>*NH»0^ [ » C^*(C^H«)AdHS2C0*]. Those 
from aleohol contain 66-74 p. e. G and 6'65H, and are therefore perhaps 
C"NH»0* = [C>»(C*H*)AdH*,-2C0»]. According to this, the crystals 
should be analogous to the compound ethers of the amidogen acids 
(vii, 220.) (Hofmann,) 



AKILin*URBA. 303 

T Cyanilide. 

Cahours a OhOBX. Oompt. rend. 38, 355. 

When pufe and very dry gaseous chloride of cyanogen is passed into 
a solution of aniline into anhydrons ether cooled with ice, a crystalline 
deposit is formed, consisting of hydrochlorate of aniline which continually 
increases; and the filtrate eyaporated over the water-hath, leaves cyani- 
lide in the form of a viscid mass which solidifies as it cools* 

Reddish suhstance resembling colophonium in friability, conchoidal 
fracture and translucence. It is completely decomposed by heat, yielding 
various products. Its alcoholic solution mixed with hydrochlorate of 
auiline and evaporated for some time over the water-bath^ yields cryst^lr 
Used hydrochlorate of melaniline : 

CKNH7 + CMN«H« « C^WH" 

melaniliiw. 

CyanUide is insoluble in water, but dissolves readily in alcohol and 
ether. Water added to the alcoholic or ethereal solution, immediately 
separates a viscous substance which ^dually becomes crystalline. 
(Cahours A Cloez.) IT. 



Aniline-urea. 

A. W. HoPMAMir. (1345.) Ann. Fharm. 53> 57; 57, 865 j 70, 130; 
74, 14. 

Ain9rm»i OffiM/f ^ AMUne, Carhamdt'CiirhQnilide^ tkrbanU<mid^^ 

Formation, 1, From vapour of cyanic acid and aniline (p. 253). — 
9. From dissolved cyanate of potash and sulphate of aniline (p. 253). — 
3. From volatile ohlpride of cyanogen and aniline in presence of water 
(p. 253). ---^ 4. From anilocyanio acid and ammonia (p. 302.) 

Preparation. The vapour of cyanic acid evolved from heated e3ranur]0 
acid is passed into anhydrous aniline which must be kept as cool as pos- 
sible; the resulting crystalline mass dissolved in hot water; and the 
solution filtered from carbanillde (which is produced more abundantly in 
proportion as the aniline has been more strongly heated^, and cooled to 
the crystallising point. — 2. Aqueous sulphate or hydrochlorate of aniline 
is mixed with aqueous cyanate of potash, and the aniline-urea, which is 
but sparingly soluble in water, separated from the potash-salt in the 
crystalline mass which forms after a few hours, by recrystallisation. —^ 
3. Aniline is mixed with an aqueous solution of volatile chloride o{ cya- 
nogen (obtained by passing chlorine gas through aqueous hydrocvamo acid) 
and the crystallised needles which are contaminated witn bydrocbloiate 



304 BBNZBNB : CONJUGATED COMPOUNDS OF ONE AT. C»KH*. 

of aniline and a small quantity of melaniline, purified bj animal charooal 
and two crystallisations from liot water. 

Propertiea. Colourless fusible needles and laminaB. 



14 C 

2 N 


84 

28 


.... 61*76 ... 
.... 20*58 ... 
•..• 0*o9 •«. 


Hofmann. 

61*45 

20*51 


8 H 

2 O 


.....M.... O 

16 


6*U 

11*93 








Ci<N«HW 


136 


.... 100-00 ... 


10000 



CNH^O (carbamide) + C»NH«0 (aarbanOide). 

Deoomponiians, — 1. Aniline-urea heated above its melting point, 
ffives up its ammonia with violence, solidifies into a crystalline of carbani- 
Bde and cyanuric acid, which latter may be dissolved out by boiling water. 
This mixture fuses again at a higher temperature and yields a custillate 
containing carbanilide : 

6C"N«H«0« = 3NH» + 3C«N«H»20* + C«N»H»0«. 

carbanilide. cyanuric acid. 

2. When gently heated with oil of vitriol, it rapidly evolves carbonic 
acid and leaves sulphanilic acid and sulphate of ammonia : 

CMN'HH)* + 2HO + 4S0» - 2C0» + C»NH',2SO» + NH>,2S0». 

3. When boiled with potash-ley, or more quickly when fused with 
hydrate of potash, it gives off ammonia and aniline, and leaves carbonate 
of potash : 

Ci<N«H80« + 2H0 + 2KO •• NH> + C^NH' + 2(K0,C0»). 
It is not decomposed by boiling with dilute acids and alkalis. 

CanMnatums, Aniline-urea dissolves sparingly in cold, abundantly 
in boiling water , and when immersed in a small quantity of boiling water, 
melts into a heavy oil. 

Dissolves without decomposition in cold oil of vitriol* 

Dissolves in nitric add, but scarcely more readily than in water, and 
(unlike urea) crystallises therefrom free from nitric acid. 

It doca not form any doable salt with bichloride of platinnm or any cryataliine 
compound with oxalic add. 

It dissolves readily in alcohol and ether. (Hofmann.) 



Nitraniline-urea. 

C**N*ffO« = C*»CyAdXH»,HW. 

A. W. HoPMANN. Ann. Fharm. 67, 156; 70, 137. 

Produced, together with biuitromelaniline, by the action of volatile 
chloride of cyanogen on nitraniline dissolved in ether. The resulting 
needles are purified by crystallisation from hot water. 



ETIIAKIUNE. 303 

Long yellow needled. 



14 C 


84 


.... 46*41 ... 
.... 23-20 
.... 3*87 ■*« 
.... 26*52 


Hofmann. 
46*10 


3 N 


42 




7 H 


7 


4*16 


6 


48 










C"N>H70fl 


181 


.... 100*00 





Ethaniline. 

C"NH" = C»(C*H»)NH*,H». 

A. W. Hofmann. (1850.) Ann. Pharm. 74, 128; C^em. Soe. Qu. J. 
S, 285. 

EihylunUiney Bihyhphenylamim, Vinaniline. 

Preparation, A iiiiztare of aniline and excess of bromide of cthjl, 
gently heated in an apparatus which allows the condensed vapours to flow 
back again, passes into spontaneous ebullition, and afterwards on cooling 
yields crystals of hydrobromate of ethaniline : 

C^^BJ + Cm«Br - Ci«NIP»,HBr. 

The mother-liquor retftins a portion of the salt dissolved in bromide of ethyl. If the 
quantity of bromide of ethyl is deficient, the crystals are contaminated with hydrobro- 
mate of aniline. The aqueous solution of the hydrobromate of ethaniline 
is mixed with concentrated potash, and the brown oil which rises to the 
surface removed with the pipette, dried over hydrate of potash, and 
Tectified. 

Properties. Transparent, colourless, strongly refracting oil of sp. gr. 
0*954 at 18^; boils constantly at 204°; smellslike aniline; does not pro- 
duce any blue colour with chloride of lime; colours firwood and elder-pith 
yellow, out much less strongly than aniline : 

HofuHiui* 

16 C 96 .... 79*84 ..m.... 79*28 

N 14 .... 11-67 

1 1 H 11 .... 909 9*27 

C«»NH" 121 .... 100*00 

- C"H»,C*H«,H,N. (Hofbann.) 

Decompositions. 1. Etlianiline quickly turns brown when exposed io 
the air, or even under the mere influence of light. — 2. With h^omine it 
forms a neutral (terbromaniline ^ and a basic compound. — 3. It takes fire 
in contact with dry chi^omic add. — 4. With phosgene gas it acts violently, 
forming a hydroohlorate and an indifierent oil. — 5. With bisulphide of 
carbouy it slowly gives off sulphuretted hydrogen. — 6. Cyanogen-gas 
passed through alcoholic ethaniline, forms short prisms probS'^^J ^^^^^^^^^^g 

VOL. XI. * 



306 BENZENE : CONJUGATED COMPOUNDS OF ONE AT. C^W. 

of cyanetlianiline C^N'H^^ This compound is separated in the polye- 
rulent form, on adding ammonia to the solution of the crystals in dilute 
sulphuric acid: its solution in sulphuric acid, on being mixed with strong 
hydrochloric acid deposits the hydrochlorate in beautiful crystals; its 
platinum- salt is yerj soluble. — 7. Ethaniline absorbs gaseous chloride of 
cyanogen rapidly and with rise of temperature, and then solidifies on 
cooling in the form of a resinous mixture of a neutral oil and the hydro- 
chlorate of a yolatile oily base« — 8. Ethaniline heated for two days in 
the water-bath with iodide of methyl, yields crystals of hydriodate of j 

metethaniline : I 

ci«NH» + ann - cwnh",hi. 

9. Ethaniline mixed with bromide of ethyl, forms in fiye days, and 
more quickly if moderately heated, tabular crystals of hydrobromate of 
biethaniline, the mixture acquiring first a pale yellow, and afterwards a 
brown colour : 

Ci«NH" + C<H»Br « C«NH",HBr. 

10. Similarly, ethaniline heated for two days in the wltter-bath with 
bromide of amyl, forms hydrobromate of ethamylaniline. 

CoTribincUiona. The salts of ethaniline dissolve very easily in water^ 
less easily in alcohol from which also they crystallise better. The 
sulphate and hydrochlorate have not yet been obtained in the solid 
form. 

Sj/drobromaie of Ethaniline. — Preparation (p. 305). Cxystallises from 
the alcoholic solution by spontaneous evaporation in large tables, which at 
a gentle heat sublime in needles without decomposition, but when quickly 
heated, are resolved into aniline and bromide of ethyl. They dissolvo 
very readily in water. Contain 40*24 p. c. hydrobromio acid, and aio 
therefore C"NH",HBr. 

Chloride of mercury and tercMoride of gold, added to hydrochlorate 
of ethaniline, throw down yellow oils which quickly decompose. 

Chloroplatinate of Ethaniline. — A saturated aqueous solution of 
hydrochlorate of ethaniline, added to a concentrated solution of bichloride 
of platinum, throws down an oil of a deep orange-yellow colour, which, 
after a few hours, solidifies in the crystalline form; a somewhat more 
dilute mixture deposits after a few hours, splendid needles an inch long, 
which must be washed with a mixture of ether and a little alcohol. The 
crystals are permanent at 100^, and dissolve very readily in water and 
alcohol. 

CrystaU at 100^. Hofmaim* 

16 96-0 .... 29-34 29'24 

N 14-0 .... 4-28 

J2H 120 .... 3-67 3-83 

Pt 990 .... 30-25 30-07 

CI 106-2 .... 32-46 



C"NH",HCl + PtCia 327-2 .... 100-00 

Ethaniline is soluble in alcohol. (Hofmann.) 



BIBTHANILINE. $0% 

Metethaniline. 

C"NH» = C»(C*H«)(0»H»)NH»,H» 

A. W. HoPMANN. (1850.) Ann. Fharm. 74, U2; CTiem. Soc, Qu. J. 
3, 296. ^ 

MeihyUthjflaniliM, Met^Mhyhphem^hmine, JPiormevinanilin, -^ (J^^^rvMtionf 
(p. 306). 

Etbaniline mixed with iodide of metbjl yields^ after being beated for 
two days in thcj water-batb, crystals of hydriodate of metetbaniline. 

Tbe base separated from tbe crystals smells like etbaniline^ but does 
not produce any colour witb chloride of lime. 

Its salts are extremely soluble and mostly nncrystallisable. Tbe 
chloroplcUinaU is deposited in the form of an oil which does not solidify, 
(Hofmanu.) 



Biethaniline, 

A. W. HopMANN. (1850.) Ann, Fharm, 74, 135. 

jDietkylaniline, IHethylophenylamine, Bivinanilin, — Formation (p. 306). 

Preparation. Tbe crystals which separate from a mixture of etbaniline 
with a very large excess of bromide of ethyl, are freed from adhering 
bromide of ethyl, and treated with potash as in the prepafation* of 
etbaniline. 

Properties. Transparent, colourless oil of sp. p. 0*936 at 18^ boiling 
witb perfect steadiness at 213'5^,and exhibiting with firwood and ohlorido 
of lime, tbe same reactions as etbaniline. 

Hofmanu* 

20 C 120 .... 80*54 8076 

N 14 .... 9-39 

15 H 15 .... 1007 10*22 

C»NH»« 149 .... 100-00 

- C»H»(C*H»)«,N. (Hofmaan.) 

. tke liquid remains transparent and colourless when exposed to 

the air. 

It cannot be made to take up more C*H» by heating it to lOO* for several days Iftr 
a sealed tube in contact with bromide of ethyl; only in presence of a trace of water 
crystals of hydrobromate of biethaniUne are formed. With iodide of ^^i^* * different 
action takes pUce. {vid. tfi/*.) 



ETUYNITRANIUNE. 309 

Ethybromaniline, 

C"NBrH^* = C»(C*H»)NBrH»,H». 

BihyiobromaniUne, VinebronumiUn, >— Bromaniline treated with excess of 
bromide of ethyl is quicklj conyerted into hydrobromate of ethybro* 
maniline (p. 278). 

Ethybromaniiine exactly resembles ethychloraniline. 

Its platinum salt is a viscid oil. (Hofmann, Ann, Pharm. 74, 125.) 



Ethychloraniline. 

C"NC1H*« = C»(C*H»)NaH«,H». 

BihyloehhranUine, Vineehhranilin, — A mixture of chloraniline and excess 
of bromide of ethyl, kept for some days at 100°, and then freed from 
excess of bromide of ethyl by distillation with water, leayes a solution 
of hydrobromate of ethychloraniline, on which a few drops of the base 
float. This base is completelpr separated by potash in the form of an oil 
of high boiling point, remaining liquid below 0% and haying an odour 
like that of anise-oil. 

The salts of this base are much more soluble than those of chlo- 
raniline. 

The sulphate and oxalate crystallise; the chloroplatinate does not, 
(Hofmann, Ann. Phana* 74; 143.) 



Biethychloraniline. 

C*»NC1H>* = C"(C*IP)«NC1H»,H». 

Diethylochloramline, BivinechloraniUfL — When a mixtare of bromide of 
ethyl and ethychloraniline dried in a hot current of air, is heated to 100° 
for two days, it is converted into hydrobromate of biethychloraniline; and 
from this the base is separated by potash as a brownish oil, which is 
purified by solution in ether, freed from potash by washing with water, and 
irom ether by evaporation. 

The solution of the base in hydrochloric acid yields with bichloride of 
platinum, an orange-yellow crystalline precipitate, which, after washing 
with water, contains 24*53 p. c. platinum, and is therefore C^NCIH^^ 
+ PtCR (Hofmann, Ann. Pkarm, 74, 143.) 



Ethynitraniline. 



EiAyhnitramline, VinmiiraniUn.^ From the large pale yellow crystals of 
hydrobromc^te of cthynitrauiliao obtaiued by the p.ction oi bromide of 



regarded u h;drated oiide of aniiiioiaam, ^^ 1 0*, In which one of the hrdn^n- 



11 of the ammoninm U repUced br phcDTl and two otben bj tb« biitomic molecule 

(W. GerhMdt.)]) 

Deeompoiitiont. 1. Oxanilio acid, when heated, gires off carbonio 
oxide, carbonic acid and water, and is converted into pare oxaoilide : 
2C'«NH'0" - CWHi^O* + 2C0 + 2CO> + 2H0. 

2. By boiling with dilate hydrochloric or salphuric acid, it is resolred 
into hydrocn]orat« or enlphatd of aniline, and free oxalic acid, — 

3. WiUi a boiling concentrated eolation of potash it girea off aniline. 

Combinatumt. The acid disBolves sparingly in cold, abnndantly in 
hot water. 

The OxanilaUt, which are isomeric with the isatatee, gire oS the 
whole of their aniline when heated with hydrate of potash, and a portion 
vhen boiled with potash-ley or strong acetic acid. 

Oxanilate of Ammonia. — a. Monohatie. — Beantifal lamina;, which 
disioWe sparingly in cold, very easily in boiling water, and in alcohol. 
— b. Bi-acid. — The eolation of the salt a is precipitated by hydrochlorio 
aind, and the precipitate left to crystallise. Scales, sparingly eolable in 
cold water. — The salts a and h begin to decompose at ISO", give off 
ammonia, and afterwards carbonic oxide and carbonic acid together with 
a small quantity of aniline, and leare oxanilide. 





. OryiittU. 


. 52-r5 , 
,. 5-49 , 
,. 41-78 


Unrent & Oerhardt. 










« ... 










1 

32 C. _... 

17 H 

3 N120 


182 .. 

'. Cry*tai*. 
192 

i; 

139 


100-Oa 

SS-33 
4-9l> 
39-77 


54-8 

B-0 


NH',2C''NH'0'. 


347 


lOO-OO 





Oxaniiete of Baryta. — The white crystalline precipitate, which the 
ammonia-salt forms with chloride of barinm, cryBtatlises from the solu- 
tion in boiling water, in specular rhombic scales which contain 29-15 p.c. 
barium, and are therefore CNH'BaO*. 

Oxanilate of Lime. — Obtained In a similar manner with chloride of 
calcium. Tnfts of needles contuning 10*8 p. o. calcium, therefore 
C^NH-CaO*. 

Oxanilale of Silver. — Obtained in like manner with nitrate of silver. 
White tabular crystals, which are nearly insoluble in oold, but dissolve 



C"N»H"0* + 2KO + 2H0 - CNH' + NH' + CK»0». 

Contiuned IxriliDi; with water, or treatment with dilate adds or alkalii, doei not decom- 
poie oiaoilamide, not for uample. Into oianilide and oiamide, ai it might be auppoied 
to do aecarding to the equation: C"N'H<'0' - CHNH«0* (oianilide) -<- CINK^ [or 
rather C^N'H'O'] (.oxamida). 

Oxanilomide is inaolnble in mter, but diesolTOB in ether and in strong 
alcohol. (Hofmiuin.) 



t> Amidonitroxanil. 

C'N'H'O' = C''(C*HO')NXAdH',0» 1 

Gottlieb. Ann. Pharm, 85, 38. 

OxalnophaiyHmid* (Gottlieb}, Nitraxophan/t-a^mid* (Qerhardt) 

Wbea unidonitranjliiio is dissolved in excess of oxalio add and 
tbe litjuid evaporated over the water-bath, a brown ish-green residue is 
obtained, consisting partl^of amidonitroxanilio acid and partly of amido- 
nitroxanil; if kopt for some time at 100°, it is almost wholly con- 
verted into the Utter without change of aspect : 

CIPIFO'.C'IPO' - 2H0 - C"N'H'0"'»i 

amidonitroianilic acid. 

C'lPa'O" - 2B0 - C'TPHK)'. 

Btnidooitroxanil. 

Gottlieb. 
WZ1 - 46-00 



42 .... 20-29 
5 .... 2-42 
64 .... 30-92 



CN'H'C -.... 207 .... 100-00 

H- Amidonitroxanilic Acid. 
CWN'H'O" = C''(CHO')NXAd'H'0'. ? 

Gottlieb. Ann. Pharm. S5, 38. 

Oxabcuipktnylatttic acid (Gottlieb), Xilraxoplitnyl-ojranle add (Gerhardt). 

rFtparalion {vid. f*;*.}— May also bo obtaiucd by decomposing Ihebaryta- 
satt with hydrochloric aoitL 



Ge 

71-11 

10-37 

6-66 

11-86 

100*00 1 



1 water, bu 
(Qerhardt 



iLd»H«,0«. 

im, Phys, 1 

anic acid n 
rolution oi 
'd froin ex< 
.atity of a 

II'O*. 
lution of a 



mg a 6< 
microsc< 



Laurent 
52 



ition ii 

ic acid 

acid r 

krabaD 

>d^ an 

iCO« 

and a 
spari 



an I line. 

Diasolvea readily in water, hydrocUorio awd, nitric add, alcohol and 
ether. (Laorent & Gerhardt.) 



Saccinanilic Acid. 

C*NH"0* = C"(C»H»0')AdH*,0' J 

Ladbbmt & Gbrbar&t. (1848). JV. Auv. Chim. Phyt. 24, ISO. 

Preparation. Snccinanil ia diasolred in boiliac; dilnte atntoonia mixed 
with a little alcohol; the liquid boiled till tbo alcohol eraporatea; tbeo 
nentmlised with nitric acid; and the crystals which form on cooling, 
purified by cryetalliaation from alcohol, 

Properiies. Elongated cryBlaUioe laminn, which melt at 155°, and 
on cooling solidify in a oiyatalline maas (not radiated); they redden 
litmus. 

Cryitalt. Lmtreot & Gwbardt. 

20 C 120 .... 62-18 62-15 

N U .... 7-25 

II H „ 1( .... 5-70 S-85 



[- C^W + C»H<0< - 2HO - |NCC»H')H{CH'0*Jo,^ 

DeeompoiUiom. 1. The acid heated abore its melting point ia reaolved 
into water and a sublimate of suocinanil. — 2. When fused at a gentle 
heat with hydrate of potaah, it ^Tea off aniline. 

ComlinatioTii. The acid disaolvea very aparingly in cold, more freely 
in hot water. 

From the aqueous solutiona of the Siuxinanilatei, mineral acids preci- 
pitate Buccinanilic acid in the crystalline form. 



SwxtTtaniiale of Ammonia.— Entaaglei cryatals, aoloble with tolerable 
facility in water. 

The acid disaolves in poiath. The ammonia-salt does not precipitate 
chloride of calcium, and forma only with a concentrated solution of 
chioride ^ barium, a slight precipitate which dissolves readily in hot 
water. With fij-rvut tails it forma a yellowish- white, sparingly soluble 
precipitate; with eupric sulphate, a light bine insoluble precipitate; and 
with nitrate of lUver, a white, Hkewiss insoluble precipitate, which 
contains 36-2 p.c. ailyer, and ia therefore C^NH'^AgO*. 

The aoid dissolvea very readily in alcohol and ttker, and cryatalliaes 
therefrom. (Laurent & Gerhardt.) 



IfALANIL. 319 

centric silky fibres. Crude suIpbosncclDanil may be nsed in tbe prepa- 
ration; for when it is dissolved in ammonia, the imparities soon separate^ 
and a coloarless solation is obtained. 

The Ammonia-salt melts at 165°, giving off a large quantity of 
ammonia^ and an oil is obtained which, when dissolved in boiling water, 
yields crystals of snlphophenylamide. It is very soluble in water; 
dissolves also in alcohol. 



20 C 

2 N 


120 

28 


.... 43-80 
.... 10-22 
.... 5-11 
.... 11-67 
.... 29-20 


Gerhardt & Chiozsa. 

441 

10-3 


14 H 


14 


5-2 


2S 


32 




10 


80 











0»N2Hio(NH^)S»0>... 274 .... 10000 

The aqueous solution of this salt treated with a few drops of hydro* 
chloric acid, yields splendid needles, which melt between 155° and 160°| 
but have exactly the same composition as the original salt. 

The Silver-saJt C^NH^AgO^", is deposited on adding nitrate of silver 
to a solution of the ammonia-salt^ in beautiful needles containing 28*7 p.c. 
silver. (Gerhardt & Chiozza.) 



V. Malanil. 

O»NH»0« = C»(C*H»0*)NH*,0«. » 
E. Arppb. Ann, JPharm, 96, 106* 

PhenyUmalimid€t Nitride qf Phenyl and MaXyl, 

Formed, together with malanilide C^N'H^^OS by melting a mixture 
of malic acid and aniline : 

C"NH7 + C8H«0W - 4H0 - C»NH»0«i 
and : 

2C^W + C?H»Oio - 4H0 - C«N«HWO«. 

When the fused mixture is kept in a state of gentle ebullition for about 
two hours^ a brown syrup is obtained, which solidifies on cooling, and when 
boiled with water, yields a nearly colourless solution of malanil and a 
coloured residue containing malanilide. The solution when evaporated 
yields malanil in tbe form of a granular mass, still kowever mixed with 
malanilide, from which it is purified by digestion in hot water and filtra- 
tion. Tbe solution is then further purified by treatment with animal 
charcoal, and evaporated to the crystallising point. 

From a hot concentrated aqueous solution, malanil separates on cooling 
in delicate needles grouped together; also when its alcoholic solution is 
evaporated; sometimes however it forms nacreous laminae, and from a very 
dilute aqueous solution, it is deposited in very thin iridescent rectangular 
prisms. Melts at 170°, and when heated between two ^atch-glaaeea, 
forms a slight mealy sublimate. 



Malanilio acid dissolves in alcohol, and epariuglj in ethtr. (Arppe.) 

IT. Citraconanil. 

C"NH*0* = C"(C'»H»0')NH*,O'. ? 

GoTTiiBB. Ann. Pharm. 77, 277. 

PAtnyUeiiraeo^imitU, Nitrii* tf P^nifl tnid CUraeonyl, 

Preparation. — 1. By mixing anhydrooa citracooic acid with aniline. 
The mixtnre becomea very hot, and if kept for some time at the, 
temperatnre of the water-batfa, solidifies into a mass of ciTgials of' 
citmconanil. — 2. By boiling or concentratins over the water- bath, an 
aqneona solution of citraconic acid mixed wiui aniline. The cendeocr of 

citrBCOnic 4dd in presence of aniline to form this bod;, ii to great, that dtncoiMte of 
■niline cumot be obtaiDed bj adding: aniline to ■ lolatioD of citniconic add or of add 
dtraeonate of ammonia. — 3. By distilling a mixtare of aniline and mesa- 
conio acid. .— 4. By the action of heat on citraconanilio acid. — The 
compound obtained by either of these processes, is contaminated with a 
small quantity of a pitchy substance from which it may be pariSed by 
ctyst&llisation from boiling water. 

ProptrUei. — CryBtallises from its aqueons solntion in shining needles, 
which, when they separate from a dilate solution, are often an inch in 
length : they are brittle and easily pulverised; inodorons. The compound 
melts at 86°, forming a colourless oil nhich sinks in boiling water. Heated 
above lOO", it volatiliaes readily, and in smalt qaantities may be'snblimed 
without decomposition, being then deposited on the sides of the vessel in 
Golontless crystals. When slowly evaporated, it exhales a faint odour 
of roses; bnt larger quantities of the vapour have a sharp odonr which 
excites coughing. The boiling aqueous solution also exhales an odour of 
roses, mixed however with that of aniline, which indicates a slight decom- 
position; from the same cause, a slip of firwood immersed in the solution 
acquires a yellow colour. The eolations of citraconil are not altered by 
chloride of lime. 

Gottlieb, 

22 C 132 .... 7058 70^S 

N _..„ U .... 7-48 7-69 

9 H ....„ „.... 9 ..„ 4-B2 4-91 

4 O _ 82 .... 17-12 16-95 

CNHiCK 187 .... lOO-OO 100-00 

- C»MH' + CUHH)! - 4HO; majbe regarded u n{^||^ that Is, a* am- 



Citraconanil is sparingly Bolable in waifr. 

TOL. XI. 



22 C _ 132 .... «-65 47-57 

3 N 42 ..„ IS-lfi „ 1505 

7 H 7 .... 2-53 2-54 

12 O 96 .... 3466 34-84 

C^N'H'O" 277 .... 100-00 10000 

Maybe resided mN{^;1^^. 

The oompoDad ia not attacked by acids; bat alkaline caibonaiea 
decompose it, producing, first an alkaline citracobinitFatiilate, and after- 
varde DinitrauiliDe (p. 292), and an alkaline oitraconate. 

Diesolvee very spariaglj in miier, but abundantly in alcohot, espe- 
cially when hot. (Qottlieb.) 



1- Citraconanilic Acid. 

C^NH'-O* = C"(C«'H'0')AdH',0*. J 
Gottlieb. Arm. i'Aarm. 77, S60. 
Aeide phtafl-eUraeeiumijtu. 

Obtained in the form of an ammonia-salt by boiling dtraoonanil with 
dilute ammonia fui about a quarter of an hour. If the boiling be stopped 
before that time, the conversion is incomplete; if it be continned much 
longer, the acid is resolved into oitraconic acid and aniline. When the 
actiou is supposed to be complete, the liquid is supersaturated with acetic 
acid, whereby the citraco nan ilia acid is separated as a crystalline preci- 
pitate, which ie washed with cold water and recrystallised from a hot 
mixture of e^aal parts of ether and 80 per cent, alcohol. The first 
crystals deposited from this solution consist of pure citracoQanilie acidj 
the remainder are contaminated with citraconanil. 

Small shining orystala, whose solution has an acid reaction. 



22 C 132 ..„ 64-39 64*40 

N 14 .... 6-83 

11 H 11 .... 6-36 5-64 

6 4B .... 23-42 

C?^H"0' 205 .... 100-00 

[=. C"SH' + CH'O' - 2H0 - ^CC^')'K'(C"'^'°*)|o'.] 

The acid is very instable; when melted, it is reaolyed into water and 
oitraeonanil. 

1 a 



soluble in w»t«r. Dried at 170°, it conbuDs 2808 p. & Wyta. 

ItaeonanilaU of Lead forms a white curdy predpitate, resembliDg 
ftbioride of leadj wben left for eome time in the liquid, it arraoges itself 
in beautiful crygtalline geodes. 

ItaeonanilaU of Copper, C*'NH"'CnO*, Is obtained by mixing the 
solution of the Hodi^salt with sulphate of copper, in the form of a pale 
blue crystalline precipitate oontaining water, which it ^ives off only at a 
high temperature. At 160°, the ^t aeaumes a bright bluish green 
colour, and is then found to contain 1684 p.c. of cnprio oxide. 

Jlaamanilate of Silver, — White cryatolliiie precipitate, which dis- 
solres in boiling water somewhat copioasly, thongh with slight reduc- 
tion, and ciystallisea on oooltng iu bni<ad abiniog DMdles. 

Gottlieb. 

22 C ™ _ 13» .... 42-31 42-47 

N 14 .... 4 48 

10 U 10 .... 3-21 3-37 

Ag lOB .... 34-61 34-80 

E O 48 .... 15-39 

CWUXAgO' 312 .... 100-00 

Bf repealed erjstslliutlon, thii iilt taffen i pcenllir ilteralion, beiiig conTcrted 
into porceitin-lilce gruiulea of another aalt which haa not been farther eiamiiwd. 

The acid diseolres in alcohol more freely than in water. 



% Gitracobinitranilic Acid. 

C?'N'H»0" = C"(C"H»O')AdX'H',O*. » 

OoTTLiRB. Atm Phaiin. 65, 24. 

CilracoHdmilrmtiUanre, Aei4t iaMropkt»sl-eitrawna«uqiu- 

Obliuned asa soda-saltbyhoilingdtracobinitranilwith adilote solution 
of carbonate of soda, care being taken not to continue the ebullition too 
long, because the anil would then be resolved into binitraailine and 
eitraconio acid (p. 323). On adding bydrocblorio acid to the liquid after 
cooling, citracobinitranilic acid separateain the form of a yellow crystalliue 

trecipitate, which, when several times reorystallised from alcohol, forma 
rond, nearly colourless needles, contaminated however with a dark yellow 
substance wnich is very difficult to Eeparate. 

Silwr-uilt, C^N'H'AgO", — Precipitated on adding nitrate of silver 
to a solution of the acid neutralised with ammonia, in the form of ft pitU 
yellow precipitate composed of crystalline scales. When dried in Taono 
over oil of vitriol, it contains 27'60 p. c. silver, the formnla reqniring 
26-88 p. & (Gottlieb.) 



deoom position »nd aublimea with tolenble r^idit; xi 140°, but does not 
boil till it is heated to ftboat 300°, at which lemperatare it suffers partial 
decompoeition, bnt sablimoa for the moat part unaltered. — • Very impure 
pyrotartanil may tbns be parified hy slow distillalioii. 

Afppe. 

22C 132 .... 69-84 6981 

N 14 .... T-41 

11 H 11 .... 5-82 6-92 

*0 32 .... 16-93 

C^NHi'D*..,,, 189 .... lM-00 

[- CWHI + C««H»0« - 4HO - N {cua','*'.] 

Strong nitric acid converts it into pTrotartonitranil. 

It diesolrea in cold aqueous <^ali« without alteration, but when 
heated is oonverted into pjrotartanilio acid. By fusion with hydrate of 
potash or soda, it is resolved into aniline and pyrotartaric acid. 

Dissolved bat sparingly in water, even at the boiliujir boat, but readily 
in alcohol and eihtr. The addition of alcohol greatly increases the solvent 
power of water for this compound, without preventiiig its separation as 
the liqnid cools. (Arppe.) 



f ■ Pyrotartonitranil. 

0*N*H'W = (?\C"H'0*)NXH',Q*. t 

ARPfX. Aim, Fhara, 90, 144. 

PjfTOtartrtinitraiiit, f/ilropiinyl-pyrofarlrimide. 

Obtained by dissolving pyrotartanil in very strong nltnc acid and 
precipitating by water. It then separates in the form of an oil, which 
gradually solidifies and may be purified by orystalUsation from boiling 
alcohol. 

Long needles united in spherical groups. Melts at 155°, and solidifies 
n a crystalline mass at 153°. Voladllses without deoompositiun when 
arefally heaf ' 



carefally heated. 



22 C 132 .... 56-41 563i 



10 H 10 

8 O 64 

c'wa'°o* «i 



11-97 



PYROTARTONITRANILIC ACID. 329 

baryta- water. With sulphate of Tine, it forms a dond after some time 
only; with seiquiehloride of iron, an oranffe-yellow precipitate; with sul- 
phate of copper a bluish green; and with mercuric chloride a white 
precipitate. 

The AmmoniorMlt is obtained by boiling pyrotartanil with ammonia. 
It dries up to a radiated mass. Dissolyes easily in cold water, but when 
boiled with water, it is decomposed and gives up its ammonia. 

The Fotash-talt resembles the ammonia-salt and dissolyes very readily 
in water. 

The Sodorgalt dries np to a confusedly crystalline mass. 

The Barytchtalt, when left for some time in the drying chamber, takes 
the form of crystalline grains. 

The Idme-salt forms dull silky needles. 

The Leadrsalt forms a white precipitate which becomes glutinous by 
boiling, but when left to itself, acquires a granular and crystalline 
character, and then requires a rather high temperature to melt it. It 
dissolyes in boiling water and in acetate of lead. 

The fSilver-saU^ C^N'H^*AgO^ is precipitated as a white pulyemlent 
body, which dissolves in water and separates by evaporation in small 
round crystalline masses of the same composition. Contains 34*36 p. c. 
metallic silver. 

Pyrotartanilic acid dissolves readily in alcohol and is precipitated 
from. the solution by water in the crystalline state. Dissolves readily 
also in ether. (Arppe.) 



IT. Pyrotartonitranilic Acid. 

C"N«H"0»'> = C»(C"H'0»)AdXH»,0* f 
Arppe. Ann. Fharm. 90, 145. 

Pyrotartranitranilic acid, Aeide nitrophinyUprotarframique. 

Preparation, By the action of alkaline carbonates on pyrotartoni- 
tranil. When that substance is introduced into a rather dilute and 
boiling solution of carbonate of soda, a yellow solution is formed which 
on cooling deposits crystals of )3-nitraniline (p. 288), but retains pyrotar- 
tonitranilate of soda, from which the acid may be precipitated by nitric 
acid. It is thus obtained in yellow flakes, which may be purified by 
boiling with animal charcoal and recrystallisation. 

From a saturated solution it is deposited in microscopic rhombic 
tables with angles of 60"" and 120^ It melts at a little above 150"". 

Dried ever oil qf vitriol. Arppe. 

22 C 132 .... 52-38 ........ 52-46 

2 N 28 .... 11-11 

12 H 12 .... 4-76 4-89 

10 O 80 .... 31-75 

C«N2H»08 252 ... 10000 

Pyrotartonitranilic acid is converted by boiling iieith alkaline cax- 
bonates into /3-nitraniline. 




■v.^ 



and when heated with water, rise 
whicb Bolidifiea on cooling. ~' 



g. — The chloroplatinate is precipitated in tho 
form of an noctuons mass, which crystalliaea only after a oonsiderahlo 
tjme, and when a portion of it has niffered decomposition. (Hofmann.) 



MethamaniUne. 

C^NH" = C"(C"H")(CH')NH*,H». 



' itethglamflBpiaii/laiHia* *• 



Produoed in the distillation of metethamaniline. 

Oil having an agreeable odour. 

The chloroplatinate is a otjBtalline precipitate whidi contains 15'81 
p. e. platinnm, and is therefore ONH^.HGl -f FtCIl (Hofmann, Ann. 
Fharm. 78, iS-) 



BtiiEiiDiuiiliiifl. 
C^NH" = C''(C"H'>){C*H»)NH',H». 

A. W. HoFMAMM. (1850.) Ann. Phann. T4, 156, Cham. 3oc. Qu. J. 



Vintmylanllln, SlittamglmilUr, BlAflamylepitns/Umint. 

Preparation. — A mixinre of amaniline and exeees of bromide of 
ethjl {vid. tup.), or of ethaoiline and excess of bromido of amy) (p. 306), 
or of iodide of amy), which acts most qnickly, is heated in the water- 
bath for two daye, and the alkaloid separated from the orystallised 
hydrobromate of etharoaoilinc in the ordinary way. 

Properties. — Colonrless oil, boiling at 262°, therefore only i" higher 
than amaniline. 

The U}/drobromate and ffj/drocAhraU of Blhamaniline cryetallise. 
The former is resolved by distillation into ethaniline and bromide of 
amyl: 

C^NH'i.HBr fc C"NH" + C»UUBr. . 

The Chloroplaiinate is precipitated in the form of an orange yellow 
viscid liquid, which solidifies in crystals fnsible at 100". (Hofmann.) 



The clear mixture of ethamaniline C»(CWH")(C*H»)NH», with iodide 
of methyl OH'I^ heated in a sealed tube in the water-bath, separates 
into two layers^ the lower of whieh continually increases, and on cooling, 
solidifies as a mixture of hydriodate of metethamaniline and hydrio- 
date of ethamaoiline. By dissolving the mass in water; setting the solu- 
tion aside, and separating it from the undecomposed iodide of methyl; 
digesting the solution with oxide of silyer; filtering from the iodide of 
silver and excess of oxide of silver, and the separated eUiamaniline 
(which is insoluble in water), — a solution of metethamaniline is obtained; 
uid this, when evaporated, leaves a hydrate, which is resolved by distilla- 
tion into water, olefiant gas and methamaniline : 

C«NH» 2HO = 2H0 + C<H* + C»<NH» 

The ehlaroplatincUe is a pale yellow, non-crystalline precipitate which 
contains 24-11 p. c. platinum, and is therefore C*Nk»,HCl -h PtCl*. 
(Hofmann.) 



Ethaniline-urea. 

(?«N»H^K)» = C»(OH*)CyAdH',H«0». i 

WuBTZ. (1851.) Compt. rend. 32, 417. 
Pkenyeikyhurea - C«N«(CMH«)(C<H»)HP0«. 

r The solution of aniline in cyanurio ether, (ix 459), the formation of 
which is attended with great rise of temperature, solidifies on cooling in 
a crystalline mass : 

C"NH7 + OT^HW - CWN«HMO». 

The compound is slowly decomposed by potash into aniline, ethyl- 
amine and carbonic acid. (Wurtz.) 

C«N«H»0« + 2K0 + 2H0 a C»NH' + C*NH7 + 2(K0,C0»). 



f . Valeranilide. 

Chiozza. (1852.) N. Ann. Ckim. Phy$. 39, 201. 

Pkmkyl'tdUromid€» 

Obtained by the action of anhydrous valerianic acid upon aniline. 
The mixture of the two substances becomes very hot, and after a while 
solidifies in a mass of beautiful crystals ol valeranilide, which may bo 
purified by recrystallisation from boiling alcohol. 



Tbe tails ar« very nnstable, all of them, exceptiBK the platinum-salts, 

oning Bpootane — -'- — -———'- *i— -— -ui— .- .^....^..a «- 

lolio aolntioD. 



decomponing Bpootanoonsly on expMure to the air, either in aqueous 
in i^coholio aolnti 



HydrochloraU of Biphenanilirie. — When itrong hydrochloric acid is 
added to pore bipbenaniline, the base remains oily at firet, but, on addition 
of alcohol of 93 per cent, suddenly solidifies ana forma a crystallino salt, 
which may be purified by washing with absolute alcohol. Shining laminee, 
having a slight tinge of ted. Tolerably stable when protected from air 
and moisture. Dissolvee easily in water atid common alcohol, less easily 
in absolute alcohol and anhydrous ether. 

Chtoroplatinale of Biphenaniline. — Separates on mixing the alcoholic 
solution of hydrochforate of biphenaniUue with a moderately strong and 
neutral alcoholic solution of bichloride of platinum, as a darlc yellow, 
bulky, flocculent precipitate, which may be washed with alcohol of 
05 p. 0. The salt is permanent in the air. It dissolves in alcohol of 75 
toSO'p. c. : and separates when the solution is evaporated over oil of 
vitriol, in brown crystals belmging to the regular system and having a 
glassy lustre. 

Oawwutin (mmi). 
S« C. .». llS-0 .... iV9» 41 iA 

N 140 .-... 8-1(1 

16 H 160 .... 3-5S „ 8-52 

Pt 990 .... 2i-86 2318 

s CI loe-a .... 23'6i 



C»NH«,HC1 + PtCP Uia .... 100-00 

BiphenaniUM with BieUoride of Platinum. — Separates as a bnlky 
precipitate, when an alooholic solution of the base is mixed with an alco- 
holio and perfectly neutral solution of biohloride of platinum. Has a 
somewhat brighter colour than the chloroplatinate, and dissolves in the 
same manner in water and in hydrated alcohol. Absorbs moistnrs ftvm 
tbe air when recently precipitated) bnt remains unaltered after drying. 

GBtimoDD {mean). 















Pt „.. 


B»0 




C-NH^PtCP. 


4U-8 



M>r be regu-ded u lltUtrid* ^ plalinotriphnglanmonitm - (fltta^Pt.CV, or 
taehioride cMoroplalino-tHplnnylammoniam — C'n|5„. },CI. 

Biphenaniline combines also with mercurie chioridt and nitral* of 
fifvn-. The merauy-ooinponDd crystallises in lamitue but decomposes 



Connoted Compotmdt of 2 At. CNH' or a timitar Nucleut. 
The Ducleiu contains 24 C and 12 H or other aDbatvieea. 



MiTBCBERUOB (1834). Pogg. 32, 224. 
ZiNiK. J. pr. Chem, 36, 93. 

A%abe»tid, Axahmol, BticMoffbemrid, Aui^ime. 

PrepanUum. 1. In distilling a mixture of the alcoholic eolntioiu of 
taitrobenzene sod potash, a red liquid passes over tovards the end, which, 
on coolinj; solidifies in a crystalline mass. This mass is pressed between 
paper and recrystallised from ether. (Mitscherlicb.) — 2. The mix to re 
of aKobenxene and aniline obtained bj tlie dry distillation of azoxibenzene 
is freed from the greater part o< the more volatile lUiiline by fractional 
distillation, pressing the residne betireen paper, anc^ crystallising it from 
alcohol. The small quantity of azobeniene wbicJa passes over With the 
aniline, separatee ae a neavy oil when the aniline is'dissolved in hotdilnte 
inlpburio aoid. {Zinin.) — T 3. When nitrobenKene is treated vrith iron 
tornings and aeetic acid, as in B£champ's process for tbe preparation of 
aniline, bdt with the proportion of iron codsiderably greater tban tbat 
which B&bamp recommends (viz. 3 pts. iron to 2 pts. nitrobenEone and 
2 pts. Boetio Boid, p. 247), tbe first portion of the diatJUate consists prin- 
cipally of aniline mixed with a smalt <^aantity of nitrobeniene, but the 
last third is a dark red liquid which solidifies in the neck of the retort 
and in the condensing tnbe as a beautifully crystallised mass of azoben- 
iene. The best product b obtained by using 3 pts. of iron to 1 pt. of 
nitrobenzene and 1 pt. of aoetia acid. The red crystalline mass is washed 
with hydrochloric aoid to remove adhering alcohol, then with water; 
dissolved in boiling aloohol; and the red crystalline laminte which sepa- 
rate on cooling, again dissolved in alcohol and recrystallised. (A. Noole, 
Cheau Soc Qu. J. 8, 292.) — 4. Benzidine treated with nitrons acid 
vapours is converted into atobeniene. (Noble), f. 

Propetiia. Large red otystals which melt at 85°, boil at 183°, and 
distil withont decomposition. (Mitscherlicb.) 









Uitscherlieb. 


Noble. 


2<C 


... 1*4 
... 28 
... 10 


-.. 79-12 ., 
.... 15-39 ., 
.... 6-« ., 


79-16 .„, 

l*-95 

, S-45 .... 


79-19 .... 79-02 










C»<N»H»..... 


... 182 


.... 100-00 ., 


99-S6 




..p«p«edb,(3)i 

TOL. XI. 


».b7(4). 




% 



waahea with oold ftlcohol, till the liquid runs throagn oolourlesa; then 
dissolved in boilinz dilate unmonia; and the scales of pnie benzidine 
which are deposited as the filtrate cools, &re dried in VBcno over oil of vitriol. 
BeDEidine may alao be obtained from osoxibenzene and hydrosnlphate of 
ammonia. (Lament & Oerh&rdt.) 

Propertiet. Snow-white scales having a silvery lustre. Become! 
somewhat duller at 100"; melts at 10S°, formiag a nearly oolourlesa 
liquid, which at 108° or 1 12°* solidifies into a brownish- white orystallino 
mass. Inodorous; its solutions have a biting peppery and hitter alkaline 
taste; permanent in the air. 

Dritd in a ttrtam ^ tir at iOV. HitAi. 

M C 1« .... 79'£6 78-02 

2N.._ „ 28 .... 15-22 14-79 

12 H 12 .... 6-S2 6-66 

CWH" IS4 .... lOO-OO 99-47 

Dtcomponti&nt. 1. Beniidine heated above its inciting point turns 
brown, begins to boil, and sublimes partly undecomposed, partly in 
resinous decomposition-products, and leaves a residue of charcoal. — 
2. The aqueous or alcoholic solution of benzidine or its salts, assumes a 
red-brown colour when chlorine gas is passed through it, often however 
after previuoely exhibiting an indigo-colour; becomes turhidj and deposits 
a large quantity of a crystalline powder Dearly insoluble in water, more 
soluble in alcohol. — 3. Its brown-red solution in strong nitric acid 
aesumee a lighter colour and gives off nitrous fumes when heated, and 
afterwards yields with water red-brown flakes, sparingly soluble in 
alcohol, together with a sapematant yellow liquid from which ammonia 
still throws down a considerable quantity of brown flakes, imparting at 
the same time a blood-red colour to the liquid. — 4. Nitrons acid converts 
it into azobenKne. (Noble.) 

Oamhmaiiont. BeaEMIne dissolves very sparingly in coM voter, bat 
so abnndanttv in hot water, that a solution sataratcd while hot solidifiea 
it a solid pulp on cooling. 

It forms with acids, white, easily erystalHsing moIu, which are pre- 
cipitated by caustic ammonia and potash or their carbonates. — Auominf, 

u is bcre dans, with Laurent & Geriiirdt (Campt. ehim. 1B49, 166) that tKDiidlne 
- ONiH", and not, with Zioiii, th*t it i« C"NH<, aU id mIU mtut bo ngwM M 

PhMphaie of .5nmt£ine. —Ordinary phosphoric acid added te a dilute 
aqneons solution of benzidine, throws down small nacreous Bcalee, and 
from the concentrated soluUon a slightly crystalline powder. The salt is 
as little soluble in water as the sulphate. 

Sulphate of Benzidine. — a. Bi-add. — Precipitated by sulphuric acid 
from a very dUute aqueous solution of bensidine, in the form of a dull 



lapa, permanent in the air, not changing at 100°, diwolring with some 
ifficnlt; in water and aloohol. 



aec les 


6t-3I ... 
10-22 
6-11 ... 
23*36 


ZiidD. 
... 61-46 


H H „ „. 1* 


... ft-39 






C«1PH>*,C«H»0" 274 


.. 100-00 





groi 
diffi 



Tartrate of £nmdint. — White ahiuiug lamine resembling benEJdine, 
bnt mote eaaUy soluble in water, 

Benzidine dissalvefl readiJv in aiaokol, and etiU mon readily in <Aer. 
(Zinin.) 



Azo^benzene. 

ZiKiN. (184.5.) J.pr. Gkem. 3S, 88. 

WuRENT & GsaBAaoT. Comp. Aim, 1849, 417; aUo Ann. Pkarm. 
75, 70. 

Ataayhenai, Aiexydifune. 

Preparation. 1 pt. of palveriied hydrate of potash is added to a 
solution of 1 pt. of nitrobenzene in a tenfold Tolome of alcobol, the 
Itqaid boiled as soon as the heat spontaneously developed has subsided; 
the brown needles of azoxybenzene which already separate ou cooling, 
collected; the remaining liquid distilled till it separates into two layers, 
ip 202 ), and the upper brown oilr layer decanted and washed witb 
water; it then solidifies after a few hours in a mass of needles of impure 
aioxybeniene. These crystals, together with the needles previously 
obtained, are strongly pressed between paper, and purified by several 
crystallisations from alcobol and ether. The purification may be acce- 
lerated by passing chlorine through the brown solation in hot alcohol till 
it turns yellow. (Zinin.) 

Propertle$. Yellow, shining, four-sided needles, and (by spontaneons 
evaporation of the ethereal solution) prisms an inch long, as hara as sugar, 
and easily friable. Melts at 3S° into a yellow, strongly refracting liquid, 
which, at a temperatare immediately below 36°, lobdifles in a radiated 



Oyttal* driti 
21 C „ 


ertile/vilrioL 
. 144 .... 72-72 .. 
. 28 .... 14-15 .. 
. 10 .... SOS .. 
. 16 .... 8 08 .. 


Zinia. 
72-65 














CWH^O" 


. 198 .... 100-00 .. 


IWM 



KitraEobfliizeiifi ' 

C^N'H'O* = C*N'XH*. 

ZiMiN. (1845.) J. pr. Chatn. 36, 103. 

Ladhemt & UBRaABDT. Compt. chiiK. 1849, 417; also Jnn. Pharm. 
75, 73. 

Nilravtbenxid, Nitriaadifimt. 

Preparaiion. 1. The cTTrtalline ma^ma prodaoed \>j the action of 
fomiDg nitrio soid on asobenzene \a drained in a filter ptngged with 
aebeatas, and afterwards on a brick to free it from the inothn-Iiquor; the 
residue disaolred in strong boiling alcohol; and the yellow nitrazobaDzene, 
which is more readily soluble in alcohol and ether, separated by repeated 
eiystallisation from the binitraEobeniene which orystallisea mnch more 
easily. (Zinin.) — Azobenzene is gently heated with fuming nitric acid; 
the liqnid left to cool after the action is finished; the mother-liqaor 
decantod from the yellowish-red mass of needle-shaped crystals thns pro- 
dnced; the crystals washed with ordinary nitric acid, tfaen with a little 
water, and boiled with alcohol; the oil decanted [from the binitrasobeo- 
lerte )]; and the needles which separate therefrom, washed with a small 
-nantity of alcohol and ether to remore an oily prodnet. (Lanrent & 

Propertia. — Slender needles of a dull straw-yellow oolonr. Palo 
orange'yellow, somewhat laminated needles, fusing mora readily than ' 
binitraiobentene, and crystallising as the liquid cools. (Lanrent & 
Qerhardt.) 

Laoreot & Oerturdt. 

2* C lit .... 63-« 62S 

3N „ 42 .... 18-50 18-1 

9 H ™ 9 .... 3-96 3'9 

4 32 .... 14-10 15-5 



z 



. 10000 1000 



It dissolres in alcohol less readily than azobenxene, bnt more readily 
than binitnzobenzene. (Lanient & GerhardL) 



Nitrazozybenzeue. 

(?«N»H'0» = C»«N»XH*,0'. 

Ztsm. (1845.) J. pr. Cheat. 36,99. 

Laurent A GBasARDT. Compt. cMjo. 1848; also Ann. Pharti^, 
75, 71. 

Nilmjoxi/bmrid, NUrcaaiydi/nm. 



C"N'H»0' 2?2 .... 100-00 

Boiled with hydroenlpbate of ammonia and with alcohol, it is con- 
Terted iuto dlphenine. (Laiirent & Gerhardt) 

C^N^H'O' + 12HS - aC'N'H' + BHO + 123. 

It dissolres withoat decomposition in boiling nitric acid, and sepa- 
rates therefrom in finer cryetala than from alcohol. (Laurent & 
Gerhard t.) 

It is nearlr insolable in cold, and very sparingly Eoluhlo in boiling 
alcohol and ttker. (Zinin.) 



Bioitrodiphenamic Acid, 
C"N*H"0" = C^X'Ad'H'.O*. 



Binilrodifunamt'dure, BinitrodiphilnamhuStire, Acide iinitrodiphinamique. 

The hUck-brown mass of needle-shaped crystals obtained by gently 
heating hinilrooarbolio acid with hydrosulpbate of ammonia (p. 200), is 
boiled with excess of acetic acid, the liquid filtered hot to separate 
sulphur, and the acid left to crystalliae from the filtrate. 

Blnck-browD, thick, six-aided needles with four lateral edges of 131° 30' 
and two of 97°; they yield a brown powder and give off their 4 atoms 
of water of crystallisation between 100° and 1SU°. 

Cryilati wilh 4 Aq. LanTent & Gerbardt. 

21 C „ 1*4 .... 41-86 42-0 . 



16 H 10 .... 4-65 4-6 

16 128 .... 37-21 36-9 

CMN'H"0'» + 4Aq 344 ... lOOOO 10000 

The crystals when heated, first give off their water, then melt, 
yielding a sublimato of a few Uminte and a small quantity of a brown 
oily distillate, and leave a large quantity of charcoal which takes fire at 
a somewhat higher temperature. 

The deep red solntion of the acid in aqueous ammonia gives off the 
ammonia when evaporated, and leaves the pnre acid. 

The browD-red solution of the acid in aqueous potash yields the 
potaeh-sivlt by spontaneoos evaporation, in deep red crystAlUne nodules 



ikMID08ULPH0nENZ£NB. . 347 

of beat, ditflolye it in small qnAntitj; ao likewise do oUoZifM carbonaies^ 
and without evolution of oarbonio acid. Hot alcohol dissolree it readily. 
(Gericke.) 



% BinitroBnlphobensene. 

C«N»H*S«0» - (?*X«H>(SO»)*. 
Gericke. jlnn. P/^arm. 100, 211. 

Formed, together with tbe preceding compound, by the action of 
fnming nitric acid on sulphobenzene, or more abundantly by the action of 
a mixture of fnming nitric acid and oil of yitriol on the same compound. 
It ia purified from the mononitrated compound by means of hot alcohol, 
in which it is but sparingly soluble. 

Small white rhombic tables having a silky lustre. Melts at 164% and 
solidifies in a crystalline mass on cooling. Sublimes without decomposi- 
tion at 320°. 

Gericke. 



mi-m. ^f ........•■..•.•.••••1 

2 N 

8 H 


28 

8 


.... -m'v t .... 

.... 91 

• ••• m O ••■• 

• ■■• A" ^ ••■■ 

.... 31-2 


.... 3*0 


2 S 


32 


.... 10-5 


12 O 


96 




(?«N«H8SH)» 


308 


.... 1000 





This formula being completely divisible by 2, it might appear as if the com- 
pound should rather be regarded as nitrosulphobensene, C^XH^SO* : but the double 
formula is justified, or rather necessitated, by the composition of the preceding compound, 
and also by that of the platinum-salt of the derived compound biamidosulphobenzene 
(p. 348), the formula of which does not admit of being halved. 

Binitrosulphobenzene, heated on platinum-foil, bums with a sooty 
flame. It is not altered by caustic alkalis or alkaline carbonates, or by a 
mixture of hydrochloric acid and chlorate of potash. StUphide of ammo^ 
nium converts it into biamidosulphobenzene. 

It is insoluble in water, soluble in strong nUric aeid, but not in dilute 
acids. It dissolves but sparingly in alcohol and ether^ even when heated. 
(Gericke.) 



f . Amidosulphobenzene. 

C^^NH^SK)* = OAdH»{S0«)«. 

H. OsRTCKB. Ann. Fharm. 98, 389; 100, 210. 

Formed by the action ofsulpbide of ammonium on nitrosulpbobenzeno 
(p. 346). The alcoholic solution of that compound mixed with sulphide 




44 C I«-0 .... 44-9 .,„.-. 45-! 

2 N ™ 2B0 ..„ 8-7 

14 H 14-0 .... 44 4-9 

2 CI 70-B .... 22-0 21-5 

2 S 32-0 .... 100 

4 O 32-0 .... 100 

C"N»H'>S'0',21ICI.. 3208 .... lOO-O 

ChloroplatlnaU. (?'(Ad)»H»(SO')« 2HC1, PtCl*. Brown-reJ, iodis- 
tioctly cryetallioe precipiute, which is itfleoted by heat ftnd hy aolreDU 
in the same inaiDDer aa the platinum-ialt of amidosulphobeDieiie. Con- 
tains IDS p. c of platinam. 

Amldomlphobeiiteae md biunidoiulphobenMiie treated with iodide of tlhyl at 
100*, yield merelf Tcd-broirn, unctnooi, micryiUDi»»blB bodiei, which do not form anjr 
nrj definite prodactt with udda or when treated with oxide of tiller. (Qerjcke.) t- 



Carbanilidd. 
C"K'H''0' = C"CyNH"',H'0". 

A. W. HoPUANN. Ann. Fharm. 57, 26fi. 

Formation. 1. When aniline ia mixed with anilocjanio acid (p. 302). 
•— 2, In the decotapoaition of Miiloc3ranio acid by wnter (p. 302). — 
3. Ia the decomposition of aniUne by phosgene gas. — 4. In the decom- 
position of aulphocaibanilide (p. 351) by caustio potaah. — 5. In the dry 
iliatillation of ouiline-nrea (p. 304), melanoximide (p. 3S7), oi monoxalate 
of melaniline (p. 355). 

Preparation. The orystallioemftas obtained bypaasingpIioBgeDegiia not 
oontainiDg any free chlorine through aniline, is treated with boiling water 
to extract hydrochlorate of aniline, and the residue crystalliaed fram 
alcohol. — 2. Vapour of cy&nio acid is made to act on aniline, which 
mnat be kept hot, and the caibanillde aepanted from the aniline-urea. — 
3. Aniline-nrea ia subjected to dry distillation. The needles which per- 
baps sepatate with a reddish tint are euily decolorised by animal 
cbarcoal. 



Propertiei, Wbite silky needles which melt at 205°, and distil 
without decomposition; they are inodorous at ordinary temperatures, 
but hare a sufibcating odour, like that of benioio acid, when beated. 



Jfee^ti. Hoftauim. 

2e C 156 .... 73-58 „ 73-48 

2 N „ 28 .... lS-21 13-07 

12 U „. 12 .... 5-66 S-84 

2 16 ■- 7-55 7-Bl 

C*N»H"»0« 212 .... 100-00 lOO-OO 

Uetanerie with the alkaline body, flsTine. 



2< C 


._... IM .. 


_ 6S-4a ... 

1228 ., 

. 5M ... 

14-04 ... 


Bofmun. 
88-28 




















C^N»H"S». 


,...„ 22a , 


... 10000 _, 


100-04 



Deeompotitiotu. 1. The aolntion of (ralphooarbanilide tn oti of vitriol, 
when gently heated, luptdlj cfvea off carbonic and anlpharoua acide, and 
if then mixed with water, Bolidifiee in the form of anilosDlpbnric acid, 
leaving ft mother^ liqnor clouded by sepuation of onlphnr : 

C"N»HaS> + 4H0 + 480" - 2(C"NH',2SO^ + 2CO> + SHS. 
The Bulphnretted hydrocen tbaa liberated ia resolTed, however, with thtt 
excess of oil of vitriol, into anlphuroue acid and salphar. — S. Sulphooar- 
banilide fhaed with hydrate of potash gives off a large quantity of aniline 
and leaves earbonftteof potuh and enlphide of potassium : 

C«N'H''S» + 2H0 +■ 4K0 - 2C"NH' + 2(K0.C0=) + 2KS. 

3. By alooholic potuli, it is slowly conrerted inb) nlphide of potasfinm 
and beantifal needles of oarbanilide; and similarly, aflei being diawlved 
in alcohol, it is conveited by atercurio oxide into black sulphide of met- 
eury and oarbanilide: 

C^N^H'^S* + 2K0 - !KS + C"N'H''0«. 

It is not decomposed by dilute acids or alkalies, or by alooholic Iodide, 
bromide, cliloiiae, or cyanide of mercnry, 

Cimlnnationt. Sulphocaibanilide dissolves sparingly in water, bnt 
readily in alcohol, and crystallises from & hot-nturftted uoobolio solntion. 
(Hofmann.) 



Helaniliud. 

C"N'H" = CK!yNAdH',H*. 

A. W. HoPiLunc. (I84B.) Ann. Pharm. 67, 12»; 74, 8 and 17. 

Formation. In the deoompositian of aniline by cblorlde or bromldt of 
^anogen (p. 253). 

J'reparation. An exoaes of moistened cyanide of mercury is intro- 
duced into bottles filled with chlorine gas, and, as soon as the colonr of 
the chlorine lus oompletely dieappeared (free chlorine would produce 
terchloraniline and terchlorocarbolic acid), the gaseous chloride of cya- 
nogen is transferred from the bottles, — by means of an aspirator, throaeh 
a tube adapted to the mouth of the bottle, and having a narrow tube 
next to it for admitting the air, — into a bottle oontuning dry aniline, 
which beoomea very hot, acquires a dark colour, and thlckeoB into a 



tiiius liyilrocLIorato of biobloromelaniline. — 3. When hromitu is added 
to aqueous hjdrocUlorate of melaniline in the manner last described witli 
reference to chlorine-wtter, the filtmte deposits, on evaporation, needles 
of hydrochlorate of bibromomelanilina^ and the mother-liqnor mixed 
with a larger qoantity of bromine and evaporated, yields transparent, 
yellow, oily drops which crystallise on cooling, and probably consist of 
tcrbromome Ian! line; for the red precipitate, resinous at first, bnt after- 



wards becoming crystalline, which their solution in hydrochloric a 
forms with bichloride of pUtinnm, contains 15 per cent, of platinum. 
— Bromine acting in excess on hydrocblorate of melaniliue, forms a 
rcsinoQs substance still richer in bromine. — 4. Alcoholic iodine added 
in excess to hydrochlorate of melaniline, throws down nearly the 
whole as a block viscid mass, which, when the qnantity of iodine is less, 
is precipitated in smaller amount, while ondecomposed melaniline remains 
in solution. — 5. Fuming nitric acid suddenly mixed with an equal quan- 
tity of melaniline, produces great heat, rising even to explosion attended 
with slight fuming; and, when gradually added, prodncas, according to 
the duration of the action, orange-yellow crystals of aa alkaloid with 
violet iridescence, and lemon-yellow prisms of an acid which furnts 
scarlet salts willi alkalia Moderately strong nitric acid, added in great 
excess or heated, likewise exerts a decomposing action. — 6. Cyanogen 
gal passed through an alcoholic solntion of melaniline, is abundantly 
abaoroed; and thia liquid, if then enclosed in a bottle, deposits bicynno- 
melaniline, the oilour of cyanogen changing at the same time into that 
nf hydrffcyanic acid, while the brown mouier-liquor contains other pro- 
ducts of decomposition. 

CoM^natiojts. Melaniline dissolres sparingly in cold water, somewhat 
more abundantly in hut wat«r, and crystallises therefrom on cooling. 
It dissolves readily in bUalphide ^ carbon. 

iSa^io/A/Wani^'nf.— Melaniline, being but a weak bosr, does not 
precipitate ferric salts. It dissolves in acids Tery readily and with sligbt 
evolution of heat, and neutralises them completely. The raits are colour- 
less or slightly calnnrcd, mostly crystallisablo, and taste very bitter; 
with firwood, chloride of lime and chromic acid, they do not exhibit the 
coloariag produced by aniline -solutions. They are precipitated by 
ammonia and more completely by potash of soda (also by the carbonates, 
with evolution of carbonic ncid, yielding a white, qnicsly crystallising 
precipitate), but not by auiline; neither does melaniline precipitate ttiii 
aniline-ealts. 

Phoipkate of Melaniline. — Very easily soluble in water, and crys- 
tallises therefrom but slowly, 

Svlphate of JUelaniline. — Rhombic laminffi nnited in stars. After 
drying at 100°, they contain 18-42 p. c HO, SO", and are therefore 
C*'N'H'',HO,S0'. The salt dissolves sparingly in cold, abundantly ia 
hot water; dissolves also in alcohol and ether. 

ff^drioJaU of Melaniline. — Concentrated bydriodio wid convert! 
melaniline into an oil, which sinks to the bottom and iraduaUy solidiBei 
TOL. XI, 2 a 



hftvin^ a golden lualre; in more concentrated Golutions, ft coploae yellow 
precipitato is immediately produced. The salt dissolves eparinKly in 
water, more freely In alcohol, very easily in ether, which, when ahakea 
up with water in which the i^t is suspended, rieee to the snrface of the 
water in the form of a deep yellow solution; and when the liquid is 
evaponted, the salt ainks to the bottom as an oil which solidifies in 





CFptlBb. 


SN 

















18-2S 28-Bl 

7-M 

B'SS 2-67 

3601 as'7l 

S5-e3 



C*N^",HCl,ioCl' .... 552-fl .... 100-00 

Chlonplatinate of NtlanHine. — Precipitated on mixing hydrochlorate 
of melaDJlioe with bichloride of platinum, first as a pale yellow crystal- 
line powder, after which a portion separatee in indistinct orange-yellow 
crystals, which are likewise obtained by diesolying the precipitate in hot 
water. Dissolres ^aringly in alcohol, and still more sparingly in 
ether. ' 

CtfttaU, Holmann. 

' 26 C , _ 156-0 .„. 37-39 _ 3721 

3N 42-0 .... 10-07 

14 H 140 .... 8-36 S-6S 

Pt 990 .... 23-73 aS-48 

3C , 106-2 .... 25-45 25-49 

C«N»a»,Ha,PlCl» 417-2 .... 100-00 

Oxaldtt of Mtlanii'me. — Melauiline forms crystals with excess of 
oxalic acid. These crystals melt when heated, give off; with violent 
ebullition, equal volumes of carbonic oxide and carbonic acid, sm^llinK 
strongly of anilocyaoio acid; ^ield » distillate of aniline and a beautifiU 
crystalline sublimate of earbanilide; and leave a clear viscid mass, which 
on cooling solidifies to a resin reeembling that prodaoed from heated 
melaoiline (p. 35%). The sftit dissolves sparingly in cold water'or alcohol, 
readily in boiling water or alcohol, but is nearly insoluble in ether. The 
crystals contain 29 73 p. c CHW. 



30 C „....„ IM ., 


,„ GS-H ... 
.. 13-95 

4-99 ... 
.. 21-27 


Hofiiutiti. 
60-35 


15 H 15 .. 


620 






C»N'H'',C<HK)« .... 301 ., 


... 100-00 





Helaailiue dissdves readily in wood-spirit, alwAel, ether, acetoRe, and 
n oUm hodijlxed and volatile. (Holiaftnii.) 



ammoniA s white oryatalline precipitate, wluch CFyBtalliaes from hot 
sloohol in irhite scales. The b&se tastea very bitter iu tta solutioua. 





Cfyil,U. 






26 C _.... 


~ 156 


.... 42Z8 ... 


«-37 


3H „ 


*2 


.... 11S8 




2 Br 


_ 160 , 


.... 43-3S 




11 H 


n 


.... 2-n ... 


2«> 


<?*N»Br»H" . 


369 , 


..„ lOO'OO 





The oomponnd heated abore its melting point, ffives off pnre brom- 
aniUne in the form of a colourless distillate, which solidifies in a yellotrisb 
crystalline mass, leaving- a resinoiis mass similar to the residue obtained 
in the dbtillation of melaniline (p. 352.) 

Btbromomelaniline is nearly insoluble in water, but dissolves in 
alcohol and etber. 

Its hydroehlomie crystallises in white silky needles groaped in stars. 
These crystals, wbeu iinmcrsed in a sniall quantity of boUing water, melt 
into an oil which solidifies in the crystalline form on cooling; lliey 
dissolve sparingly in water, and contain 0'19 per cent, of hydrochloric 
acid; hance they are C?'N'Br'H",HCl. 

The hot-saturated solution of tbe hydrochlorate forme with bichloride 
of platiuum, an orange-yellow precipitate, which, on cooling crystallises 
ill golden-yellow soalee, nearly insoluble in water, sparingly soluble in. 
ether, somewhat more in alcohoL (Hofmann.) 



Pbaimtm^lt. 


.. 27-12 ... 
... 7-32 
„. 27-81 
.. 2-08 ... 
.. 1721 ... 
... 18-46 


Hofmana. 


3 N 420 ., 








Pt 990 . 


1711 






C"K*B[=H'',HC1 + PtCP.... 575-2 . 


,.. 100-00 





Bichloromelamline. 

C"N'C1»H" = C«CyNAdCl'H',H». 

A. W. HoPMiKS. (1848.) Ann. Pharm. 67, 146; Cfiem. Soe. Qu. J. 
1, 298. 

WbcD chlorine-water is gradually added to hydrochlorate of melani- 
line, till the turbidity no longer disappears on agitation (p. 352), th» 
filtmte evaporated and cooled, yields hydrochlorate of bichloromelaniliue 
in white stellate needles, or by further evaporation, as a yellowish oil 
which solidifies in the crystalliDe form. From tbe solution of this salt 
in water, in which it is sparingly soluble, whereas it dissolves mure 
readily in alcohol and still more iu etiier, ammonia precipitates the baM> 
in snow-white flakea, which separate from the alcuUoUc solution iu hur>l 
ci-ystalliue himiuo;. 



DtcompotHioTu. Binitromelaniline when heated gives off a yellow 
Tapour, which condeusee la brown oily drops chiefly coDEiatiiig of nitra- 
Diline and gradually crystallisingj and leaves in the retort a brown 
resinous mass. 

Comhinationa. Bioitromelaniline ts insolable in water, even at ths 
boiling heat. 

MydTOcIUorale of Binitromdanilme. —'F\t,i shining needles, sparingly 
soluble in water; they contain 1082 p. o. hydrochlorJo acid, and are 
therefore C"j?J'H"0',HCl. 

Ckloroplatinale of BinUromeUmiline. — The solution of the hydro- 
chlorate forms wilb bichloride of platinum, a yellow crystalline precipitate, 
which contains 19-58 p.c. platinnm, and is therefore (?';s''H"0',HCI,PtCl'. 
It bums with slight detonation when heated, aod dissolTes sparingly in 
water and alcohol, bnt not in ether. 

The mlfhate form* white orosts which dissolve readily in water. — 
The nifcate is sparingly aolnblfr. — The tmiiaU forma easily soluble crys- 
talline grains. 

Binitromelaniline dissolves sparingly in aloAol and still less in ether. 
(HofinanD.) 



Cyaniline. 

CTJ'H" = C«Cy»Ad»H',H». 

HoFHAKK. Ann. Pharm. 6a, 180; 78, 160; Chm. Soe. Qu. J. 1, 160: 
2, SOO. 

fbrmation (pp. SS2, 2a3). 

Preparation. Cyanogen gae is passed through a solntion of aniline 
in a six-fold quantity of alcohol, till the liquid smells strongly of it, but 
not longer; and the resulting crystals are freed from the mothei'liquor, 
which eoloors them reddish yellow, either by repeated washing yiith cold 
alcohol, or by washing them twice with that liquid and subsequently 
dissolving them in dilute sulphuric acid, filtering frora a red crystalline 
powder, precipitating the p^e yellow filtrate by ammonia, and crygtal- 
lising the pale yellow pnlvernlent precipitate once, twice, or three times 
from a large quantity of boiling alcohol, tiU colourless lamtnn are 
obtained. 

PropertUt. Colourless, silvery, iridescent lamina, which do not 
volatilise without decomposition, even in company with vaponr of water; 
they melt between 210° and 220°, and solidify in the cryaialline form on 
cooling; they are heavier than water; inodorons and tasteless; neutral. 
The acid solntions of this base do not colour Grwood yellow; neither do 
they turn bine in contact with chloride of lime, or give the precipitate^ 
oi aniline with chroniioacid, 



Comhinationt. CTaniline is iDsoInble ia vater and disaolves bat 
Bparingly in bmtlphide of carbon. 

Saitt of Cyaniline. — Theae Baits must be bronglit to the solid atate as 
qoicklj M poaaible, before tbay decompose. Tbej are not prodaoed by 
posaing cyajiogen gu through alooholio solutions of anilloe-ealts. 
According to tne formnla C^N'H", they mnst be regarded aa biacid salts. 

Sulp^te of Cyaniline. — Very soloble, deoomposea by eTapontioo, 
like the hydrocblorate. 

Sydriodate of Cyaniline. — Reaombles the hydrocblorate, but quickly 
deposits iodine on exposure to tbe air. 

Hydrobromate of Cyanilirte. — Cyaniline ifl dissolved in boiling dilute 
bydrobromio aoid, and the filtrate immediately mixed with an eqnal 
qnaatity of concentrated bydrobromic aoid, wliicb separates or^atala, to 
be washed, first vilh concentrated bydrobromio acid, then with other. 
Tbe valt is very much like the bydrocblotat« of cyaniline. 



Crytlalt. 


1D9 .. 
56 ., 
16 . 

ISO . 


42 .. 
14 
4 .. 
40 ... 


HohUDD. 










2 Br 


39-28 


C»N*H'*,2HBr 


. 400 . 


100 





MydroehloraU of Cyaniline. — Tbe boiling vcllow solution of cyanilioe 
in boiling dilute hydrochlonc acid, is filtered hot and immediately mixed 
with an equal quantity of fuming hydrochloric acid, which decolorises it, 
and soon oanaes the separation of a large quantity of colourless crystals, 
which mnat be washed witb hydrochlorio acid and then with ether. 
These crystals, which have a very nweet taste, are permanent when dry, 
bat decompose in the moist state, becoming at the same time insoluble, 
iu water. Their aqueous solution yields by evaporation, the s-ime 
products of dooompoaition as the direct solntion of cyaniline in dilute 
hydrochlorio acid (p. 360). Aniline added to the aqueous aolution of the 
crystals, preoipitates the cyaniline as the weaker base, and acids throw 
down the oiystals in their original atate. The crystals dissolve vitb 
great facility in water and iu alcohol. 





Cryiial*. 


. M-05 ... 
. 18-02 
. B15 ... 
. 22-78 ... 


Hofmutn. 




.. 50-0 ... 
... 160 ... 

.. ;o8 ... 




18 H 


5*45 






C^N'HVUCI . 


... 310-8 ... 


. 100-00 





Nitrate of Cyanilint.-~T\»e solution of oyaniltne in boiling dilute 
nitric acid, yields on cooling, white needles, which maybe crystallised 
without decomposition from boiling water, dissolve sparingly in cold 
water, and to a sdli leas amount in alcohol and etber. 



Crflat*. 
28 C 16B ., 


.. 46-16 ,., 
... 230; 
.. 4-40 .. 

... SC-37 


4C-38 






12 O 96 . 




U!'N'H",2HO,2NO* .... 364 , 


... 100-00 





Proptrim. Needles having a verj pale yellow colour, and not 
atile witkont deooniDaaiiinn- 



volatile vitloDt deoompoaition. 



C»N'Hi» _. 363 .... lOO-OO 

DecompotUiont. I. Bicyanomelaniline when heated, giree off aniline 
and hydrooTanate of ammoaia, and learea a resin which becomes car- 
boniseil at a higher temperature. — 2. Ita pate yellow eolnti on in mode- 
rately strong hydrochloric acid (from which at the first moment, ammonia 
throws down Dnalt«red bio janomel aniline) becomes ooloared in a few 
minotea (instantly if somewhat concentrated or if heat is applied), and 
gradually deposits melanoximide (p. 266), in the form of a pale yellow 
cryetalline powder, while the motncr-liqnor retains sal-ammoniuc, the 
nitrogen in which unonnts to 10'U7 per oeot. of the hioyaaomelaniline 
employed : 

C'N'H'* + 2HC1 + 4H0 - (?WH"0' + 2NHKa. 

Otlier acids, eren Ttgetable acids, act like hydrochlorio acid, the more 
qniokJy as they are more concentrated. — 3. The boiling alcoholic eolutioit 
of bioyanomelaniline mixed with excess of hydrochloric acid, acquires a 
transient yellow coloor, and on oooline deposits white needles, sal- 
ammoniao being formed at the same time and the liquid losing ita 
colour. 

GombinaiioM. fiicyancmelaailiDe is Insolnble in water. — It dissolTea 
in oold dilute acidi, even in vegetable aoids, and thence appears to be a 
veak base; bat in consequence of ita rapid conversion into melanoximide 
and ammoniacal salt, which doee not allow the precipitation of unaltered 
bicjranomelaQiline by potash or ammonia, excepting at the first instant 
after solution, it is impossible to obuin crystallised salts of this base. 

Bicyanomelaniline dissolves with tolerable bcility in alcohol. 



Chlorooyanilide. 

C*N*C1H'* = C~Cy'Ad»H',HCI. 1 

Lacbbnt. (1842.) If. Ann. Chim. Phyt. 22, 97; also J. pr. Ckem. 
44, 187j abetr. JT. J. Pkarm. 10, 308. 

FormatUm and Preparation. Solid chloride of cyanogen (ix, 463) 
in the state of powder is gradoally introduced into a fla^ containing 
aniline diesolved in Inkewarm water and the requisite quantity of 
aleobol; and the ehlorooyanilide which &lls down as » white powder. 



solved. (UerUardt.; —'2. ihe solution of oyanilina in excess of dilate 
bydroohlorio acid is oTttporated over the water-bath; the dry residue 
treated vith cold water to remove sal-ammoniac and bydrochl orate of 
aniline, then with boiling water to dissolre oxamide and oxanilainide; 
and the oxanilide which remains andissolved, is pariGed by solution in 
boniene, filtration, and evaporation, and l>y washing the crystals with 
alcohoL (Hofmann.) 



PropaHet. White nacreonH scales, which melt at 245" and solidify in 
a radiating mass on cooling; they boil at 320°, giving off a sharp vapour 
like that of benioic acid, and distilling for the moat part withont decom- 
position, and sabljme at a gentle heat in iridescent lamins. 



28 C 


.... 168 ., 


... 7000 .. 
... 11-67 .. 
„ 600 .. 
.. 13-33 .. 


Gerhardt. 
6S-63 ., 
12-40 
513 . 
12-84 


Hottainn. 
... 69-60 


12 H.._ 

4 O 


.... 32 . 


... 5-00 


C»N'H"0« .... 


.... 2*0 . 


.. lOO-OO .. 


10000 





Deeompositiont, I. Oxanilide enbjected to rapid dittillatuin, yitildB a 
email quantity of oil containing a trace of anilocyanio acid, which gires 
it a powerful odour. — 2. .finwimf acta violently upon oxanilide, giving 
off hydrobromtc acid and forming a substance which dissolves in ether 
and crystallises therefrom. (Gerhardt.) — 3. Hot nitric octtf gives off red 
vaponrs. (Gerhardt) Aqueoos chromic acid and other dilute acids do 
not act upon oxanilide, even when heated. — 4. The solution of oxanilide 
in warm oil of vitriol effervesces when strongly heated, girin|> off carbonic 
oxide and carbonic acid in eaual volumes; it then turns slightly brown, 
and on the addition of a small quantity of water, deposits a large quan- 
tity of anilosulphnric ncid in the form of a white crystalline powder 
(Gerhardt): 

OSWH^O* + 2H0 + 4S0> - 2(C"NH',2SO») + 2C0 + 2C0". 

fi. Oxanilide diilillfd with anhydrous phoBphoric acid or chioriJe of linc, 
gives off carbonic oxide and carbonic acid, and is almost completely car- 
bonized; nevertheless, especially with phosphoric acid, the oil which 
smells of anilocyanio acid passes over, together with sublimed cnrbani- 
llde, in larger quantity than when the oxanilide is distilled alone. 
(Hofmann.) — 9. Vapour of oxanilide passed over red-hot time, yields a 
body which may be regarded as C"N*H". (Hofmann.) — 7. Oxanilide 
heated with dry lime gives off aniline, and becomes partially carbonised, 
and sometimes heated to redness. (Gerhardt.) Anhydrous baryta elimi- 
nates Bcaroely any thing but aniline. (Hofmann.) Oxanilide hented with 
Etash-lime, hydrate of potash, or concentrated (not with dilute) potash- 
j, is resolved into a distillate of aniline and a Ksidne of oxalate of 
potash. (Qerhaidt.) 

CornbinaliMu. Oxanilide does not dissolve in water or in dilnt« 
aolphnric acid, even at the boiling heat. (Gerhardt.) 

Oxanilide dissolves in slightly heated oil of ntriol, and is precipi* 
tated therefrom without alteration by water. (Gerhardt.) 



■e then reaolTcd into 2 At. 

3C"N'H"0» = 2CMNH'0" + C^T^WKf. 

^r hut, rendae & gito off iBrbanilide, ) 
)rinic Kdd uid water, and learet the reiidoe 

CHrBPCf = C!»N>HiK)> + C^WH". 

2. Melanoximide is but slightly decomposed hj dilute salphnrio or hydro- 
chloric acid; bat when dissolved in alcohol and boiled with coQcentrated 
hydrochloric acid, it is resolved into oxalic acid, melaniline, and needlea 
not yet fully examined, the solution at the same time acquiring a deep 
ye\lo^ colour, and emitting a powerful odour of ftnjlocyaaic acid. — 
S. Ita aloofaolio solatioa BoIidifiM in ooDtaot with ammonia or potath, 
either of which takea np a large quantity of oxalic acid, forming crys- 
tals of melaniline; and a rimilar decomposition takes place gradually in 
ita solntion in aqnfloits ammonia or potash, eapeciolly when concentmted. 

Combinationt, Helanoximida does not disBolre in water or in aqueous 
adds. 

In aqoMtts aMnumia or pctatK it dissolves at first without deoompc- 
sition, and may be precipitated from the solution by acids; afterwards 
decomposition (3) tahes place. 

Its solntion in weak alcohol forms with nitrate of iHver, especially on 
addition of a small quantity of ammonia, a light yellow ainnrphoaa pre* 
cipitate, containing from 2S'4 to 2857 aud 30-5 per cent, of silver. 

It dissolves spuringly in boiling alcohol, and ciystaUisoB therefrom in 
crusts, (Hofmann.) 



SuccinanUide. 

C*N»H»0* = C^C«H'O')NAdH*,0*. 1 
Laorkkt k Qbrhasst. (1848.) JV. ^nn CkifH. Phys. S4, 182. 

Succinic acid mixed in a flask wiUi exoeai of aniline, and heated for 
ten minutes to the melting point, till water and the excess of aailine are 
driven c^ Tields a liquid which on coolingeelidifiea in spherically grouped 
needles, and from whieh boiling water extracts sncnnanil, while enocina- 
nilide remains nndiesolved and may ht parified by crystallifation from 
alcohol. 

It eryetaUisea iirom the aln^oli« Mention in slender needles vhidi 
melt at 2X0°. 



32 C 


192 . 


U 

... 71'64 .... 
... 10-45 
... 5-97 .... 
... 11-94 


iDrent & Gerhsrdr. 
.... 71-5 




















C»N'H"0' ... 


...- 268 , 


... 100-00 





T It&conanilida, 
C«x'H"0* = C*^C'°H»0'}NAdH",0'. ! 

OomiEa Ann. Phamt. 77, 282. 

P&eH^l-ilaeaaamide. 

When itaeonic acid is heaied witlt excess of aniline to a tenipetatnre 
alittle abore 182°, water and ezoess of aniline distil over, andthereaidne 
on cooling solidifies for the most part in a crjstalline mass consisting 
chiefly of itaconanilide, wliich may be puri6ed br two or three cr;^talli- 
sations from boiling alcoboL It is also produoed by the action of 
citnconic acid on aniline. 

Larf^e, light, delicate scales, having a nacreons lustre like that of the 
fatty Kcids. Melts at 185°, and solidifies in a crystalline masson cooling. 
May be sublimed in small quantities withont decompoaition. Its vapour 
has a pungent odour. 



31 C 

■ 2N 


aoi ., 


... ra-ss 

.. 1000 
... 6-72 
.. 1143 


Gottlieb (mtmt). 
72-84 




















CWN*E>H>' 


280 . 


,.. 100-00 





- aC'NH' * CHK)" - 4H0. 

Nearly insolnble in cold waUr, very sparingly soluble in boiling 
waterj dissolves readily in alcohol and ether. 

Aqneons acids and alkalis do not act upon it, even at the boiling 
poiut. 

Strong tulphurie aeid dissolves it, forming a brown solnUon from which 
it is precipitated withont alteration by water. 



H- Pentanitro-itaconauilide, 

C"N'H"0^ = C?\C«H'0»)NAdX''H*0». 

Gottlieb. Ann. Pkarm. 85, 38. 

Itaconanilide dissolves in a mixture of strong nitrio and snlphoiia 
acids; and on adding water to the solution, a pnue yellow pulverulent 
body is precipitated, which, after washing with water, gives up to boiling 
alcohol a very small quantity of a substance, which crystalliws from the 
solution in small yellow scales, while the priucipat product of the reaction 
is a perfectly amorphous snbatance, which produces ataiofl) >° destitute of 
Tot. XI. 2 B 



iiquia la aiiuiea wim traier, foperBacuraieu wiui njaTOCiiJorio nciu, 
filtered hot, and the filtrate eupe saturated with ammonm. Tlie crystal- 
line alkaloid tlius precipitated ia purified either by recr^stalliBation from 
ether, or by pouring dilute sulphuric acid over it, washiu^ the sulphate of 
dipbaaine with cold water and alcohol, diegolviug It m boiling water 
coDtaiuing hydrocblorio acid, and precipitadng by ammonia. 

Properties. Yellow, cryatallind. 

Laarmt& Geriuirdt. 

12 C 72 .... 87-92 670 

2N 28 .... 26-4a 



CN^H* 108 .... 10000 

Uurent ft Qerbwat donbU the rormni*, making it (7*N<H'*. 

It diasolves with a fine red colour in hydrochloric or nitric acid. 
Ita hydrochloric acid solution forma with bichloride of platinom a 
carmine-coloured precipitate, containing : 



12 C 73-0 ' .... 23-Oe 


Unnut & Gerhudt. 


















C"N>H»,Ha + PtCl'.... 312-2 .... 100-00 




Ato^iuUut CN* 




Faracyanogen. 





JoBNSTOK. If. Ediab. J. o/Se. 1, 75; also Schw. 5S, 341. Ann Pharm. 

22, 280. 
PoLTD. BoBtLAY. /. Pharm. 16, 180; also S<^: «0, 107; also £r. Ar^ 

34, 82; abstr. Pogg. 20, 63. , 
Tbadlow, J. pr. Chem. 3Ij 220. 
Spbmobr. J. pr. Cheia. 30, 478. 
H. Delbruok. J. pr. Chan. 41, 101. 

Bttlii Cyatmgat, Sharhtrtt qfAaott, 6Uekh)hlnutqf. 

Formation. 1. When certain metallic cyanides are Ignited in close 
vessels: e.g. cyanide of mercury (viii, 14); cyanide of silTer (viii, 27); 
ferrotranide of lead. (Thanlow.) When moist cfanide of inercnri li hrated, 
tbe roidn eoataliH more tbui 2C to IN, bectaio a proportioutelT Isf ^ qnmlltj of 

2 b2 



of mercury, prodacos thick white fumes, hkving a euBboating odour and 
Gondeasiag in the form of a white hody in th^ reo«irer. This aabetance 
may be sublimed without alteratioa; it is iDodorons, permaneut in the 
air, yields when fused with carbonate of soda, » mass which exhibits the 
reactions of cyanogen aud chlorine, and dissolves in hot water, formins 
a solution which does not exhibit the reactions of cyanogen. (Delbriick.) 
Paracyanogen obtained from cyanide of silver, likewise forme with 
chlorine, copious white fumes, but no sublimate. The apparatus emit* 
the monse-Uke odour of fixed chloride of cyanogen, and the escaping 
gas has a pnngent odour probably of volatile chloride of cyanogen. 
(Delbriick.) — 4. Paracyanogen ignited in a stream of hydrogen gas, ui 
resolved into ammonia, hydrocyanic acid, and oharooal (DelbrUok) : 

OT*' + UH = SNIP + 3C:nH + 6C, 

C"T*» + lOH = 2NH' + iCTIH + 4C.> 

Nitric acid neither decomposes paracyanogen (1) nor dissolves it 
(Johnston, Delbriick.) Bnt, when paracyanogen obtained from cyanide 
of silver is evaporated to dryness with nitric acid, and the residue 
slightly heated, it assumes a light yellow colour, dissolves in nitric acid 
and may be precipitated therefrom by water. (Delbriick.) — Para- 
cyanogen mixed with chlorate of potash detonntee by heat, but not by 
percussion. (Johnston.) Sulphnr does not act npon paracyanogen, either 
when the two are heated together, or when the vapour of the salphnr 
is passed over heated paracyanogen. (Delbruck.) — Reipecting Brown'i 
■llegcil eonventoQ of paracTBao^n into lilidmn, oonpsre Smltb & Brttt [iPMt.Mag.J, 
t9,295 ; 20,1). 

Com&inolfons. Paracyanogen (1) is iusoluble in water. (Delbriick.) 
It dissolves in warm oil of vitriol. (Compve hoiretcsr Bcnelini, p. 372.)— 

The Bolntion yields on evaporation a greyish black residue insoluble in 

water; it appears to be capable of forming a crystaUine compound with 

inercuiy. (Johnston.) 

It dissolves in hot concentrated hydroeKlorie acid, forming a light 

yellow solution, which, when evaporated, leaves an abundant rciians 

insoluble in water. (Johnston.) 

It does not dissolve in nitric acid or in ammonia. (Johnston.) 

It dissolves in aqueous potash, but probably undergoes decouiposition 

at the same time. (Johnston.) 

Paraeyanide of Silver. — Remains when cyanide of silver is ignited 
In close vessels (viii, 27), as a grey, porous, very refractory mass, whiofa, 
when strnck with the hammer, acquires a perfect metallic lustre like that 
of bismnth, and becomes hard and brittle, so that it may be crushed 
to a fine powder. (Thaulow.) Greyish silver-white, hard and brittle 
(Delbruck.) 

Paracyanide of silver very strongly ignited in a retort yields nitrogen 
and cyanogen gases, at first in the proportion of 1 vol. nitrogen gas to 
IS vol, cyanogen; then of 1 : 24; then of 1 : 0'66; and lastly of 
1 : O'O. — 134 pts. (1 At.) of cyanide of silver strongly ignited m a 
retort, till the paracyanide of silver formed at first, is decomposed, gives 
o£r 20'44 pts. in the form of nitrogen and cyanogen gases (134 grm. 
of cyanide of silver yielding 04 cubic centiuietrcs of the gaseous mixture.) 



*nd e*aii buck, >nil jlelat ■ precipitate or the nine coioar, the farmatian of irhirh ii 
accelerated bj heat Tbii companad ia inioluble in water, but ioliible in caaslio 
HlkKlis, and repredpitatedby »cid»; it gife* off 10-5 p. c. water at 100". It contaioa 
carban and Ditrogen, but not Ui the proportioas to rorm paracjaaogen, tbe carboa being 
in excess, and likewiie oiygen and bjdragea. Different ijiecimenB gave reaalti varriDK 
from 4B'92 to *2-05 p. e. C; 41-62 to 4277 N; end 3Z to 3-4 H. A limilar .ub- 
ataoee ii formed br pauing ahloriDV tbrongh a aolDtion of cjuide of potaanum : the 
prodnct thai obtained giTsa 35'2 to 36'2 C; 42 30 N; and 3-00 H. Whea treated 
wiUi nitric add, it fotmi • ;reUo>compoand (Ljon Plajftir, Citm. 8«». Q. /. lili, 12S). f . 



Appendix to Pmacyanogen, 

Agqlmic Acid. 

Johnston. Sehxe. 36, 341. 

Pol. Boullay. J. Pkarm. 10, 180 ; also SiAw. 60, 

H. Delbbdck. J. pr, Cftem. 41, 161. 



Fint noticed andeiuniaed in lonta of it* relations bj Promt in 1B06 (-dan. dim, 
60, 233 ; alto ff. Geil. 3, 584), tben b; Ittaer in 1809 {BeUrage i. Oetciiekle J. 
BimuHurc), and bjr Oaf-Liuiaa in 1811 ; afterwardi lomeirhat more minutet; hj 
JobitMn nd Bonllaf i (rsqaentlr oonfonnded with pare(7aQDgen, from vbiob howerer 
it iiShn bj eont«iiiia( b^drogea', 

Formation. In mauy deoompositioDQ of o^nogan sad hydrocyaiiio 
Bcid. (rii, 3S6, 6; 387, 7; 402, 12.) 

Preparation, An aqneooa or a dilute aleoholio Bolntioo of oyKnogen 
or aqueoua hydroCTanio acid ia left to itself for some time — b«Bt after 
addition of a small Quantity of ammonia or of potash — as long as tbo 
liquid, whioh gradaaity acquires a brown oolonr, continnes to deposit 
browD flakes; and tbeso flakes are collected on a filter and washed witb 
water. The water takes up a portion of tham, becoming brown thereby, 
tba solution being cansed by tbe ammonia produced in toe deoomnositioa. 
or perhaps by the ammonia or potash added. This portion may oe prft< 
oipitated by an acid. 

Special moda of preparation : 1. Concentrated .^ or better, anhy- 
dions — hydroovanio acid is left to itself til) it solidifles in a brown mass, 
wfaich is woahed with water and dried. 

2. Hydrated alcohol saturated with cyanogen gas ia left to stand as 
long as flakes are deposited in itj and these flakes areooUaoted on a fllt«r, 
the aloohol then runniog off colourless, afterwards washed with water, 
which then becomes yellow, and dried. (Johnston.) 

3. An aqueous solatioo of cyanogen is abandoned to spontaneons 
decomposition, and tlia brown precipitate washed with water, and dried. 
(Pelonze Se Richardson, Ann. Fkarm. 26, 83.) 

4. AlcohoiJo potash is saturated with cyanogen gas; the liquid 
decanted from prccipiti^tfid cyanide of potassium; get asid.* fnt aonu tims 



ifeampomwni l. Aiuimia uid (i) jielda by drv distillation, bydra* 
oyanio acid, ammoniai, Knd water, and leaves charcoal containing nitrogen. 
(Pronst}. It yields a sublimate of hydrooyanate of ammODia, and when 
more singly heated, a gae smelling of cyanogen, hnt burning with a 
bine flame, and leaves oharooal. (Boullay.) The acid (1) or (2) 
which is CN'H'O*, gives off, when ignited, carbonate of ammonia 
together with a anialt qnantity of water, and leaves paracyanogen. 
C»N*H*0* = 2(NH',C0*) + C':^'. (Johnston.) — Acid (4) when gently 
heated, gives off a large quantity of hydrocyanic acid and bydrocyanats 
of ammonia, and leaves a residue which cMitains more carbon than 
cyanogen contains, and is therefore resolved by strong ignition into 
cyanogen gas and charcoal free from nitrogen. — 2. Chlorine gas passed 
over axutmic acid, gives off white fumes having a pungent odonr and 
perhaps ooiituning volatile chloride of cj^nogen; no soblimate is formed, 
but the apparatus exhibits the mouse-like odour of solid chloride of 
cyanogen. (Delbriiok.) The acid (1) dissolves in cold concentrated ' 
nitric acid. The aurora-red solntion is precipitated by water; when 
evaporated, it leaves a pitchy residne, sparingly soluble in cold, better in 
hot water, and e«sily soluble in potash-ley, from which acids throw 
down a body resembling indigo-resin. (Bonllay.) The acid (1) dissolves 
readily in nitric add, and water added to the yellow solntton throws 
down paraeyanie acid in the form of a yellow powder. (Johnston.) 

Paracyanu! acid = C'N'O; when subjected to dry distillation, it 
gives off carbonio acid and cyanogen gases, and leaves paraayanogen. 
Mercuric paraeyanate is precipitated even from the hot solution of para- 
cyanic acid in nitric acid [on addition of mercuric nitrate!]; it is 
= 2HgO,C'N*0. Paraeyanaie of tUver is AgO,C'N*0. (Johnston.) 

The solution of asulmio acid (I) in nitric acid is but partially preci- 
pitated by water; ammonia throws down the whole of the dissolved 
matter in thick brown flakes. Lead and silver salts precipitate the nitric 
acid solution more completely than water; but the liqnid filtered from 
the silver precipitate still forms with ammonia a thick brown precipitate 
containing 3*07 per cent, of oxide of silver. The nitric acid solution of 
aiiilmic acid neutralised with ammonia as far as possible without precipi- 
tation, forms with neutral acetate of lead, a thick white precipitate; 
with copper-.salts a light green; and with manganese-salts, after addition 
of sU-ammoniac and ammonia, a light brown precipitate. When tlie 
nitric acid solution of azulmic acid is precipitated by nitrate of silver 
without addition of ammonia, the precipitate contains 31*06 p. c oxide 
of silver; if ammonia be added, immediately, but not in suffident 
quantity to produce alkaline reaction, the precipitate contains lfl'35 p. c. 
oxide of silver. These numbers do not agree with Johnston's formula, 
which requires 51 p. c. oxide of silver. (Delbriiok.) 

4. Aialmic acid ignited with carbonate of potash forms cyanide of 
potassiam. (Ittner.) 

Comiinatumt. Washed atulmio acid (I) is insoluble in mifer 
(Bonllay); (3) dissolves sparingly. (Pelonze & Richardson.) 

The acid (4) dissolves in ml of vitriol whence it is precipitated by 
water. (Thaulow.) 

It dissolves in concentrated hydrochloric aeid. (Thaulow.) 

.The acid (1) dissolves easily in aqueous ammonia oi pottuh forming a 
dark brown-red solution; acids throw down from this solution a red- 
brown powder; heavy metallic salts decolorise it and form brown 



12 C „ 72 . 


... 90 

... 10 


... 89-58 .... 887fl 
.... 10'42 .... 9-77 




cm» „ 80 . 


... 100 

Vol. 


... 100-00 .... 99-56 
Demltj. 


H.^.....:. 


8 . 


0-5IH6 


oa-Tv«w 


2 .. 







Deeompontioni. I. The oil boniB with a bright flams whioh depoaifi 
a large qaantlty of soot. — 2. Id contaot with oil of vitriol, it acquires 
a dark colour, becomes strongly heated, au<I ia resolvod into a lower thidc 
black layer containing a conjugated salphnric acid, and an upper thin 
yellow liqnid, which is not further altered by cold oil of vitriol. — PotaS' 
sium has no action upon it at 85-5". (Faraday.) 

ComHnatiOTU. The oil dissolves very spariDdy in water, very readilv 
in alcohol (whence it may be separated by water) m rtA<r and in oih botn 
Jixed and volatile. (Faraday.) 



Oxygen-nttcleut C"H*0'. 

Fyrocatechin. 

C"H"0* = CH-CO'. 

Reiksch. Repert. 68, Si. 
Wackenrodbr. Ann, Pharm. 87, 309. 
CoKBT. ZwENOEit. Ann. Fkarm.. 37, 327. 
BoDOLP. Waqnkh. J. pr. Chem. 52, 450; 55, 65. 
EisSFELDT. Ann. Pharm. 92, 101. 
Max. Ucciineh. Ann. Pharm. 08, ISO. 

PgTumoritamie acid, Phtnte or Oxyphenie acid. — First obtained by Roiosoh 
in 1839; mors exactly investigated by Zwenger, Wagner, Eiesfeldt and 
Bacbner, 

Formation. By Uie dry distillation of catechin (Reinsch, Zwenger), 
of moritannio acid, gnm ammoniacum and probably also of pcuoedania 
(Wagner), of kino (Eissfeldt); also of wood, whence it is found in wood- 
vinegar. (Bnchner.) — It doee oot oasnr la ood-Ur. (BncbncT.} 

Preparation. I. Catochin or cateohn is introduced into a retort of 
A^nrfold cvpncity, and qnicklv heated above its melting point antil it 
chars; the distillate which collects in the cooleit receiver, evaporated at 
go" till cryatals form on the surfuce, the empyrei mitio oils which become 



reddens ittmns. JUixed witti bydroclil&nc acid, it (OloaM hrwood vinlet, 
the colouring being stronger as tlie pyrooateckin is more free from 
carbolic acid (Wagner.) 

mtlimtd. fiutd. lien *uili»ied. 
12 C rS ». 65'45 G5-a5 .... 66-32 6b-il 



5-46 5-60 .... 

. 32 .... S90 9 28-8S .... 28-06 2B'63 

. 110 .... lOO-OO „ 10000 .... 100-00 100-00 



EiMfcldt, Buchncr, 
fati. dried. Jiued. tubliaud okdjiued. 
.. 65-01! M-91 68-62 6838 



100-00 10000 



Eiiifeldt'i Grit aiuifiii wu m*de with pTrocttMbin prepared from malabar-kioo ; 
the second from butea-kino. — BnchDer eipUioi the eices* of cuban and hjdrogm, on 
thu aappoiitton (hat the pTrocatechin had a imall qoantitr or a bTdrocarboD adhering 
to It. 

Pjrrocatecbiii ii metameric with bjdrochioone. 

Veeompotithnt. 1. Pyrocatecliin lums yellow when heated, and 
becomes, as appears from the preceding analyses, somewhat richer in 
carbon. It also leaves a slight black residue when sublimed. Tbis 
resiilae boiled with water, leaves au empyrenmatio resin, and yields a 
brown decootion; on evaporating this liquid, a black film forms on the 
surface and a brown black residae is left. — From tbia nddoe, alcohol eitracti 
« yelloiruh, Cnotlnceat, amarphoui lubtlaace (■imilar to Raage'i viridic acid) whois 
■qaeaai aolntion acqnira a green culonr, graduillj on eiponire to the air, bat imin«- 
diiCely on addition of potaih. The aame lolntion forma with barTta-valer a green 
precipitate ; with neotnl acetate of lead, a white precipitate which alterwarda lurni 
green; with ferroaa gaits a black; and with nitrate uf Filler a brown precipitate. 
(Zwcnger.) Pjrocatechia may be dirtilled andcBomposed eren with eiceaa of baryta or 
lime. (Wagner.) — 2. It bums with a bright flame. (Zwenger.) — 3, Its 
aqucons solution turns reddish in contact with the air, and may be evapo- 
rated without decomposition. (Zwenger.) — 4. It is rapidly decomposed 
by chlorate of potash and hydrochloric acid, yielding cbloranil. (Wagner.) 
— 5. Nitrio acid acts upon it with violence, evolving red vapours. 
(Zwenger.) The products of tbis reaction are oTalio acid and traces of 
ayellownitro-acid, probably atyphnio acid. (Wagner.) — 6. With aqueous 
chloride of lime or bichromate of potash, it forma a black liquid and a 
black precipitate. — 7. With aqueous caustic alkalis or alkaline car- 
bonates it forms a mixture which is yellow at first, then becomes greenish 
yellow, and lastly black. (Zwenger.) The change of colour, accompa- 
nied by rapid absorption of oxygen, proceeds in the following order; 
green-brown, then black and opaque; with milk of lime: green, then 
qnickly brown. (Wagner.) — The aqneons solution of pyrocatechin pro- 
aaoes a greenish precipitate with silver solution, the silver being partly 
reduced, and a dark brown precipitate with solution of gold. To bichlo- 
ride of platinum it gradually imparts a green colour and then fonas ft 



Paramtamtc acid, Anhgdroiit meconic acui. — JJlaCOTcred, in 18i}2, by 
Robiquet, who at first regarded it as anhydroua meconic acid; arterwards 
reoognised as a dietinct acid \sy Liebig, nlio firet ubMrred the furmation 
of carbonio acid which acoomptuiies the conveinoii of meoonic into 
Gomenio aoid. 

Formation. 1. By heatinj^ meoonto acid to tamperataree between 120' 
and 220°, the ohanf^e being attended with erolution of oarbonio acid i 

C"a*0" - C'H'O" + 200*. 
2. Sy oontinaed boiling of tneconicacid disgotred In water or In hydro' 
chloric acid, likewise with erolution of carbonic acid. (Roblqnet.) 

Preparai!^. Meconic acid (Liebiff), or meconate of potash or baryta 
(fiobiqnet), is boiled with a etrong mineral acid; or meconate of Itme is 
boiled with highly concentrated hydrochloric acid (Stenfaonse); or acid 
meconate of potash, produced by treating cmde nentml meconate of lime 
with very dilate hydrochloric acid, la heated with as much strong hydro- 
chloric acid as is required to dissolrc it (How), and the aolntlon left to 
crystallise. When the mere aqneoDi lolntlon of the idd ll boiled, too large ■ qiun. 
titj oF bronn ■eeondarj' prodaot ^ fonned. (Robiqaet, Lteblg.) 

Puri/icalvm. The still reddisti crystals are dissolred In a slight excess 
of hot conceiitrat«d potash; the solution filtered hot to separate a smalt 
quantity of lime; the white nodules which form on cooling, washed with 
a small qnantity of cold Water, till the strongly coloured mother-liquor is 
removed; then boiled with excess of hydrochloric acid; and the comenio 
aoid which separates on cooling, freed irom hydrochloric acid by two or 
three racrystallisBtioos from water. The still remaioiag tinge of red 
may be removed by treatment with animal charcoal. (Stan ho use.) —^ 
2i The impore acid is dissolved in a qnantity of boiling ammonia just 
sufficient to dissolve it (because an excess, as well as continued boiling, 
causes the liquid to turn brown), and Glt^red immediately at a boiling heat; 
the yeUow crystals which aeparste from the dork filtrate when left at 
r«st, washed with cold Water, and recrystsllieed from hot water; their pale 
yellow aqueous solution mixed with strong hydrochloric acid; and tbA 
oomenio acid, which is precipitated in the form of a whit4 or {>alo yellow 
powder, orystoUised from boiling water, 

•* ProperHet. Hard, yellowish, very acid, ^nuhtr crystals. (Robiqnet.) 
Prisms, laminte, or granules, having a very &int yellowish colour, 
(H»».) 

The oiTitala ore onhydrons. (Liebig.) 





Cr9.UU. 


.. 46-15 . 
.. 257 . 
.. ' 51-28 . 


Robiquet. 

^S-28 ... 

3-65 ... 

.... 51-07 ... 


Liebig. 








lo o „. 












C"H<0» . 


156 


-. 100-00 . 


10000 ... 


... 10000 



Pecompotiliong. 1. The acid, when subjected to dry distillation, 
behaves like lueconio acid. (Robiqnet.) When eomenio (or meconic) 



The lame campoiUlon vu foand bjHoir; IT, how«T«r, (h« add be nentratiMd 
vitb nmmoiiU and tnixrd with alcohol, radiating priams separata which-xive off 13-73 
p.c. water at 100°, and are therefoie C>'II\N11')0X' -t 3Aq. (How.) 

Comenate of Potash. — a. Biha»ic. — The aqneona acid balf neo- 
tralised with potash [ao a« to form tlie monoba-^io salt] yields no precipi- 
tate, bat when comploteiy neatiuliseil, deposits the eparin^Iy Buluble 
neutral [liibasic salt]. In tbis respect, o^menio acid is opposite to meconic 
acid, tlio aciil pota?L-salt of which ia t!ie less soluble of the two. 
(Itobiquet.) 

b. Monobeuie. — Ulio acU dissolved in a slight excess of boilini; 
potash'lcy yields crystals on cooling, which, after washing with cold 
water, crystallise from hut water in short, square, anhjdcoos ueedles, 
which rcddeu litmus. (How.) 





CrgttaU. 


... sr-oa ... 

,„ 1S4 ... 
., 24-30 ... 

.. 37-oa .... 


How. 








KO 


il-2 .. 


I3-8S 








CiiR^KO" 


194-2 . 


... 10000 ... 


100-00 



Comenate of Soda. — JIfonobatie. The solution of the acid in tolerably 
slroDg boiling soda-ley yields, on cooliug, nodules and prisms, wbicli, 
when washed with a small quantity of cold water, crystallise from solu- 
tion in the smallest possible quantity of boiling water, in acid, anhydrous 
four-sided prisms. These crystals dissolve readily in water, and contain 
1709 p. c, soda, and are therefore CWH'NaO". (How.) 

Comenaleof Bai-yta.—a. Bibeuic. — Chloride of barium mixed with 
a solution of the acid in excess of ammonia, throws down immediately, 
or in Tery dilute solutions, after some time only, yellowish quadratic 
needles united iu concentric groups. These crystals do not lose water 
at 100°, bnt at 121°, they give off 19-03 p. c. C (At.) water, and if then 
heated to redness in the air, burn away in a fiery clond. They do not 
dissolve in boiling water, bnt when boiled with it, are conrerted into a 
basic salt, which does not give off water at 131°, and contains 54'5 p.c. 
baryta. (How.) 





Al 121°. 


„ 23-29 .... 
.. 1-29 „, 
... 49-5S .... 
.. 2S87 ... 


How. 

s3-or 














10 


80-0 . 


41-41 


CWBtKy + 2i 


iq... 309-2 ., 


... 10000 .... 


lOOOO 



h. Monoiaiu:. — The free add doei not pndpiCate baryta-ialU. (SlcDhouf.} — 
The Mlt ii pnidQced when barfta ia boiled with eiceu of the add.— Chloride of 
barinm mixed with a cold- sat a rated aqueous solution of the crystallised 
ammonia- salt, immediately forms a crystalline precipitate, and with a 
more dilute solution, gradually deposits transparent rhombs [1]. The 
acid crystals gradually give off their 20-86 p. o. (somewhat more tlmu 
6 At) water at 100°, and melt at a stronger heat (How.) 
vor.. XI. 2 o 



0. Monooanc. — Lrystallisee, after a vhila, from a mixture of 
mlpfaate of magnesia with the cold-eatarated sutatioa uf the oryetalline 
ftmnioiiia-Balt, in amall rhombs, an<l from more dilute Bolutiooe, od evapo- 
ration, in larger cryetala which are strongt; acid, gire off 2208 p. c. 
(6 At.) water at 116°, and diasolfe readily in hot water, (How.) 



ZPHfJo/llE*. 


... 38-S2 ... 
... 270 ... 
... 10-81 ... 
... 47-S7 ... 


How. 
38 62 

1110 
4J31 


SH 6 


MgO 20 . 




Cua'MgO" + 2Aq 185 . 


... 10000 ... 


100-00 



Commat4 of Lead. — The acid and itf ammonia-calt form with nentral 
acetate of lead a yellowiah white graDolar precipitate, solable in ezcew 
of comsnic acid, bat not in acetio acid. (StenhooM.) 

Dried at IW. Stenhoiua. 

12 _.. 78 ..- ie-8» le-u 

4 H _ 4 .... 1-OS 1-16 

IPbO 2!4 .... 58-95 68-80 

10 O 80 .... 21-Oa 21-20 

C"H'Pb»0>» + 2Aq S80 .... 100-00 ....... 100-00 

A lod-ult euminBd by Robiqaet cootiiDt 51-1 p.e. oxUeof lead. 

Ferria Comenate. — Comenio aeid impnrta a brigtit red oolonr to ferric 
salte. The dark blood-red mixture of ferric sulphate with a cold-saturated 
solution of comenic add or its ammoniacal salt, becomes paler by long 
standing, and deposits small, pitch-black, shining, verr hard, nearly 
taateless crystals, which frate between the teeth, yield a dark brown 
powder, and dissolve slnwly both in cold and in hot water, forming a 
pale red eolation. (Slenboua&) 



CVy.f.b 


drit4ailO0\ 


... 34-37 .. 
... 2-63 .. 
... 19-09 .. 
... 43-91 .. 


Stenhonte. 


11 H „ 


_ 11 . 


2-9» 


Fe»0» 


80 . 


18-58 








F<?0»,2C'*H*OW + ; 


(Aq 41S . 


„. 100-00 .. 


10000 



The red miitnreof aqneous comenio acid with ferric snlpbate, becomes 
dark yellow at 65° (and gives off carbonio acid: Hour), bv convereion of 
all the sesquioxide <^ iron into protoxide at the expense oi the acid, pait 
of which at first remains nndecom posed, so that a fresh portion of ferric 
sulphate again prodaces reddening. This colour however disappears 
when the liquid is disiested for 12 honrs with excess of ferric sulphiite, 
in conseqnence of the complete conversinn of comenic acid into another 
and; hence the no longer red liquid deposits small, pale yellow, shining 
crystals of a ferrous salt (probably ferrous oxalate, as the liquid contains 
oxalic acid : How), which bum away when heated, and dissolve sparingly 

S o 2 



Coj\^a(ed Compound, 

Etbylocomenio Acid- 

CHH)" = CH'0',C»H*O». 

How. Ed, PhU. Trant. xi, 2, 225; Ann. Fhtata. 80, Sa — Furtlier. 
Ed.ir. PkiLJ. 1,212. 

VtnoeomaUe add, CMRMODtmic and, WtmionuiuSMTt, AethertomauAiire. 

Formation and pTeparation. 1. Dry hydrocliloric acid gas is pnssed 
through shaolnte alcohol at which pulveriaed comenio acid ia suspended, 
till the aoid dissolves, whiob takes place slowly; the clear liquid (which 
denoaitH nothing ou addition of water), eraporated at a temperature 
below 100°; the crystalline residue maintained nt this temperature, till it 
no longer srnelU of hydroohlotio acid ; and then left to cryatalliaa by 
oooliug from its solntion in water at nearly 100°. — 2. Pulverised 
comeiiic acid heated with alcohol and iodide of etbyl in a closed vessel to 
a temperature above 100°, forms a granular deposit consisting of an acid 
not yet examined, (perhaps Stenhouso's parcomenic acid, p. 410) and 
ethyfooomenio acid in needle-shaped crystals, which may be separated 
and purilied by rccryatallisation. The same products and not araylo- 
comcnic acid are obtuned by beating a mixtare of comenio acid, alcohol 
and chloride of amyl, to 150° for 12 hours. 

Proptriia. T^rge square needles, which begin to evaporate at 100°; 
melt at 135° into a clear hrown-red liquid which solidiBos again in the 
crystalline form on cooling; and if kept for a longer time at 135°, sub- 
lime in long, Qat, unaltered needles having the siuue composition. 
Reddens liLuius. 



16 C 


yttaif 


96 
8 
80 


.. 52-17 ... 
.. *-3!> .. 
.. «-*8 .. 


How. 








10 












C«H»0» 




18< 


.. lOO-OO .. 


... lOO-OO 



Deoompositioni, I. The acid may be boiled for a short time irithont 
alteration, bnt if boiled for a longer time, it yields free comenio acid. — • 
2. With aqneone solutions of the fired alkalies, eves in the cold, it very 
quickly forms salts, and yields free alcohol. 

C(im.binatwn». Easily soluble in water. 

When ammoniacol gns is pnssed through a solution of the acid in 
absolute alcohol, the aniiAinia-aaU is deposited in yellow silky bundles of 
nocdles, which give uff ammonia in dry air, and almost completely 
in vncuo over oil of vitriol, and leave etbylocomenio acid. 

The acid imparts a deep red cidour to ferrk'taUt. — Its eilver-tatt is 
gelaiinoua and decomposes very quickly even in the dark. 

The acid dissolves very readily in aiooho!. 

Its aqueous solution coagulates albumen. (How.) 



uf cblonDe water, and gradually depoaita orTitiUB of flaioToooinflDio acid, 
which inoreasa oa addition of hjrdroohtorio acid, and may be purified as 
in (1). The mothei-lianor become* oontiniuilly browner, and still 
depositfl brown crystals ot the aoid. 

The crystals, which eonttua 3 At. water, are dried at 100*. 



a 100*. Bo«. 

. 72-0 .... 37-81 a7-S3 

. Sa-4 .... ie-S9 „ IBTT 

S-0 .... IM 1-79 

. eO-0 .... «03 41-91 



. lOO'OO lOO-OO 



Decompotitioni. I. The aoid melts when heated, blackens, gives off 
a large qnantity of hydrochloric aoid, and at last yields a small crya- 
tnliine sublimate, probably oonsisting of paracomenio acid. — 2. By nitric 
acid, it is quickly converted into hydrochloric, oarbooic, hydrocyanic 
and oxalic acid. — 3. Its aqneous solution treated with line, slowly eives 
off hydrogen, and afterwards eoDlains hydroehlorio acid and oxide 



ComHnatioTu. Hydraied ChlorocomenU acid.— The aboYe-mentiooed 
Inns, colourless, ehininff, four-sided prisms. They ^re off 12-47 p. c. 
(3 At.) water at 100°. They dissolve both in cold and in hot water, more 
roadily than comenie add. 

The ehloncomenaia resemble the comenates, bnt diuolve more readily 
in water. 

The monobasic chlorocomenatee of ammonia, potash, and soda cryt- 
talliee readily. The bibasic salts are not obtainable. 

The ammonia-salt forms with Monde of bariwn and chloride of 
caldum, bundles of needles which appear more or less quickly according 
to the degree of concentration; — with tuipAate of maffnaia it gradually 
forma a few er^t-Us; — and with etipric tulpkate immediately a crystalline 
precipitate. — The bibasic ehlorocomenates of theee faasee appear to be alt 
amorphous and insoluble. 

The aeid celoiua ferric taUt deep rad, like oomenio acid. 

SUver-talt. — a. Sibatie. — The acid disaolred in a eligbt exeess of 
ammonia forms with nitrate of silver, yellow amorphous flakes which, 
after drying, resemble clay in appeamnoe, conBixtence and tenacity. 
The salt dried at 100° eontains j>6'85 p.e. silver, and is therefore 
C'CIHAg'O"'. When ixnited in the vr, it leaves silver together with a 
email quantity of chloride of silver; when boiled with hydrochloric acid, 
it remains partly undecomposed. It is insoluble in boiling water, Irat 
dissolves in nitric acid, from which, if h be heated with the salt, cyanide of 
silver separatee. 

b. Monobatk. — The warm aqneoos aeid added to a ndntion of nitrate 
of silver, throws down feathery crystals, which, after washing with cold 
water separate firom boiling water in short shining needles. These 
crystals give off 4-44 p.o, water at 100°. When ignited, they leave 
Bilver and chloride of silver. 



monobatie bronuieonifnaU of gUver, vhioli, after wuhiog with cold water 
and BolntioD in boiling wat«r, Bepantes to abort ehiQing prisiuE, con^ 
tainiDg, when dried at 100°, 3364 p. c oxide of silver, and tlierefure 
= C"BrH'AgO". 

The Mud is less soluble in hot alcohol than chloroconienio acid. 
(How.) 



Oxi/aa>-nvdeut C"NH»0». 

Comenamic Add. 

Hemrv How. £d. PkU. Trant. xx, 2, 225, ^itn. Pharm. 80, I>1; Chan. 
Soc Qu. J. *, 370. 

Formation and Preparation. 1. Monobarao eomenate of ammonia 
healed in a sealed tube to 199°, leaves a carbonnoeons masa from which 
water eitraets comenaiaate of ammonia, the acid of which is precipitated 
l>7 hydniohloric acid in wbtte srales. — 2. Aoneous oomenio acid is 
boiled with excess of ammonia till nearly all the ammonia ig expelled 
from the liqnid, which aseumes a blacki'h red colour; the grey, viscid, 
argillaceoDs sediment of comenamnte of smmonia mixed with coloaring 
matter, collected on a filter, and dissolved in hot water; the solution 
decomposed by hydrochloric acid not in excess; and the preeipituted 
dark brown scales of impure comenamio acid purified by repeated cryetaU 
lisatioa from hot water, and treatment with animal coarcoal free from 
iron. Chireod contuDlng iron would giie a porple colonr to the acid. 

The crystaU are dehydrated by heating to 100°. Their solution 
reddens litmus strongly. 

Atiddritd at im". How. 

12 C _- 7t .... *6-ii 46-16 

N U — 003 _. 917 

5H~ _....-. 5 .... 3-23 3-39 

8 O ™. __ 64 .„ 41-29 41-28 

C"NH*0» 165 ....100-00 100-00 

[The formaU CAdH'O'.O' vonld repr«Miit the acid u oianobatir, wherca* it i« 
bibasic, like comenic add.] 

The acid is decomposed by boiling with potash, yielding ammonia and 
oomenato of potash. 

Combinntiotu. Hydrated Comenatnic add. — Tho ah.-no-mcntioncd 
crystals; Colourless shining plates which give olT 18'81 p. c. \i At.) water 
at 100°, and diiisolvo very sparingly in cold water. 

The acid dissolves readily m hiidrocliluric acid a;id oiLor strong 
mineral aeidn, and is precipitated therefrum as comcnamilo of a 
when tho liquid is not quite neutralised with aiuniouia. 

The acid formg with most bases, bibasit and monolKuie lalU. 



OIL. - 8^ 

precipitate, whicli is partially decomposed by boiling vatcr. The acid 
dissolves in boiling alcohol of ordinary sttengtli^ btit scarcely in boiling 
absolute aloohoL (How.) 



Comenamate of £thyl. 

C"NH»0' = OH*0,C"NH*0\ 
Henry How. Ed. I^. Fhil J. 1, 212* 

Comenamie Biker, 

When a solution of comenamie acid in absolnte alcohol is treated 
with dry hydrochloric &cid f^, and the liqaicl sabsequently evaporated^ 
there remains ah oil which dries up at 100 to a solid mass, and when 
dissolved in alcohol, yields a hydrockloraie of comenamie ether, 
C*H»0,C"NH*0' -f HCl + 2H0; and on treating this compound with 
oxide of silver, or with ammonia (not in excess), comenamie ether 
is ohtaitaed in ndedle-shaped crystals containing 2 At. water; 
C*H»0,C»NHW+2H0, which they give off at 100% leaving tU 
anhydrous bther. -^ When thto solid mass abore mtBntioned in treated with water, 
comeoamic add remains andissolTed, and another portion of that add separates as A 
crystHlline powder from the solution, whioh contains hydrochloric add. 

The ether is neutral; melts to a yellow liquid when heated, is not 
altered by ammonia in the cold; and is converted by nitric acid int6 
oxalate of ammonia. It dissolves sparingly in cold tffcUer, readily in hot 
water and in mineral acids, sparingly in absolute alcohol. 

A oomponnd of this ether with hpdriodic acid is obtained hf faeatiuff 
iodide of ethyl with a solution of comenamie acid in absolute alcohol 
to \6Qf^ in sealed tubes. (How.) % 



Primary Nudeus C^B}\ 

Oil, C»H". 

GoUEBBB. (18S8.) Ann. Own. Phys. 60, 184; also/, pr. Chem. 18, 165. 

Polyearhwrs kj^drique (Couerbe). 

In the distillation of resin-oil (x, 411), there passes over, after the oil 
resembling amylene (x, 1,2) and before the oilC^'H* (xi, 370), the oil 
CH*^ which has a density of 07524, boils between 65"^ and 70°; and a 
vapour density of 2-637. (Couerbe.) 

12 C 72 87-80 

10 H 10 12-20 



C»H» 82 100-00 




together witb Hnlphario acid, there remains in solution a conjn^tcil 
euTpLurio acid which for.na witli lead-o»ide a gummy salt, the sulpho- 
valerate of lead which ij soluble in water. Vulernl ia not perceptibly 
altered by boiling potash-ley; but every drop of the oil poured upon 
melting hydrate of potash, girea off hydrogen, and solidifies into a mixture 
of valerate and carbonate of potash : 

C^H^O" + 6H0 - CWH"©* + 2C0' + 6H. 

Comhinationi. Valerol diesolves sparingly in waUr. 
It absorbs ammoniacal gat abundantly, but does not appear to form a 
crystalline compound with it. 

It dissoWes readily iu alcokd, ethtr, and volatile oili. 



Oxsym-ntuhui C"HK)*. 

Qmacic Add. 

C"H»0' = C"HW,0* 

BiaBiM. J. Chim. med. 12, 355. 

Thibbry. J. Fharm. 27, 38 1 ; also Br. Arch. 28, 55. 

Preparation. 1. Rasped gniac-wood is exhausted with alcoholj tliB 
frreater part of the alcohol distilled off from the tincture; the brownish 
white liquid which remains wiih the resin made up into a pasta with 
magnesin; the misture diatiUed to dryness, whereupon an arotaatio water 
passes OTer; the residue BuspemJed in water and mixed with sulphuric 
acid; the white substance thereby separated, dissolved in alcohol, and the 
acid obtained in needles by evaporating the liquid. (Righini.) — 2. Com- 
mercial guiac resin is dissolved in the requisite quantity of warm alcohol; 
I of the filtrate distilled off; the acid yellowish liquid fiUcrod when cool 
to remove the deposited reain; then neutralised with baryta [to wh^t 
purpose 1], and evaporated to one-half; thebafytaprecipitated by sulphuric 
acid, anv excess of which most be carefully removed hy means of baryta- 
water; tue filtrate evaporated to a syrup overthewater-bath, and the residue 
frequently shaken up with ether to extract t!ie guiacio acid. On subse- 
quently evaporating the ether, the acid is deposited in nodular masses 
containing resin, which may be purified by sublimation in small quanti- 
ties, and at a very gentle heat ^ia Mohr'e apparatus for benioio acid). 
(Thierry.) [Is it not thereby converted into guiaceue?] 

White shining needles, which dissolve in water more readily tiian 
benzoic or succinic acid, and are likewise soluble in alcohol and ether. 
(Thierry.) 

According to Peville's analysis {Compt. rend. 19, 137), the gaiacic 
acid obtained by Thierry is CH'O*, and is resolved by enblimation into 
guiacene(x, 411), and carbonic acid C"'H'0»= C-<'H"0»+ 2C0'. 

According to Franj; Jahn (JV. Br. Arch. 23, 279; 33, 258), the acid 
which exists in very small quantity in euiac-wood and in somewhat 
larger quantity in the resin, is not a peculiar acid, but merely beniuic 
r.cid. But the experiments on ita reMtions made with the impure acid 



rroptrtia. White, nnereona, thin, otten dendritio lacniDn and needles. 
(Berzelius, Pelouie.) Melts without loss of water at 115° (furming a 
cotourlesd oil which eolidiSes jn » radiated maas on cooling; Gm.), and 
boils at 210°, giving off colourless vaponrs which hare a slightly paiigent 
odour, (i'nJouEe.) Tast«s bitter (Berzelius); freeh and bitter (Braconnot); 
as bitter as salicine (Stenhonse). Does not redden litmns (Berselina, 
Stenhonse); searcelj (FeloDw); slightly (Braoonnot). — Thu reddening ii 

pmdncad odIj vheo the acid bu been tabUmed it too high ■ teniperBtnre and miy 
therefore be coDtuniaatad with ■ ToUtile udd. (SteDhoun.) Permanent in the air 
when dry. 

Bersdlu. Pclonie. Mulder. Stenhanie. 

6714 .... 66-64 .... 6748 .„. 67-18 .... &r'60 

4:; .._ 5-00 .... 4-83 .... 4-77 .... 4-7$ 

38-09 .... 38-36 .... 37-69 .... 38-05 .... 37-62 



. lOO'OO .... 10000 



Deoompositiont. I. The acid, when gently A«al«<j, volatilises for the 
most (lart nndecomposed, leaving an inconsiderable carbonaceoas residue. 
(Gm.) By repeated sublimation, it is for the most part decomposed, 
leaving a substance resembling tannin [metagallic aciA], tugetber with 
charcoal. (Braconnot.) It blackens strongly at 250°, giving off water 
and leaving mcta^llic acid. (PelooEe). — 2. When quickly heated in 
contact witn the air. It bams with a red flame, without leaving charcoal, 
(Qm.) — 3. When dissolved io water, or moistened with water, and 
exposed to the air for a few seconds, it forms » mouldy substance. 
(Qm. Braoonnot.) The solution abandoned to spontaneous evaporation no 
longer leaves crystals, but a reddish gum. (Stenhouse.) Series for djeug the hair 
(V/iniiBeT, Rfpert. S3, S2.)— i. Py roga I lie acid dissolved in aqneoos alkalif, 
absorbs oxygen, unless that gas is most carefully excluded, and forms 
solutions, which are variously coloured according to the nature and 
quantity of the alkali, and ultimately turn brown, a mouldy substance 
and perhaps also acetic acid being formed at the same time. — ]26]>ts. 
(1 At.) of the acid mixed with ammonia, absorb 48 pts. (6 At.) of oxygen, 
and form a brown liquid from which hydrochloric acid precipilatcs 
moaldy flakes without any evolution of gas. (Dbbereiner, OUb. 72, 203; 
74, 410). — The solution formed with potash-ley turns brown from above 
downwards, and leaves, when evaporated in vacuo, a block gum, wiclioiit 
crystals, which dissolves readily in water, gives off carbonic and act.'tio 
acids when treated with dilate sulphuric acia, and if somewhat concen- 
trated, deposits a few black flakes, which immediately redissolve when 
washed with cold water. (Stenhouse.) — The shades of colour are aa 
follows : With a small Quantity of ammonia: yellow; with a Urge 
quantity: red-brown. With a small quantity of poUuh : red-brown, 
afterwards brown; with a large quantity: blackish violet, changing to 
dark brown. With a erasll quantity of 6ory(a-water or «(ro7i/ja- water : 
reddish yellow; with a large quantity; violet, afterwards brown with 
brown flakes. With a large quantity of ItnM'Water : violet, ciianging 
tjaiekly to pgrple, and ultimately to brown with brown flakes; this effect 
is ptoaooed, though loas qnickly, even when the ur is completely e xcluded, 



evaporation vitb solid oarbonato ol ammonia in Toctio orer oil ot A'Unol, 
leaves a dry yellow or grey salt, wliicb assumes a brown or green colour 
in contact with the air. (BerwliuB.) Tfie acid snpersaturateJ with 
ammonia givcB off all its ammonia in vacuo. (Stonhonse.) 

With potash or loda, out of contact with the air, the acid forms very 
soluble saltsj the potash-salt forms rhombic tables. It does not form s 
cloud in barjfia or tti-ontia water. (Pelonse.) 

FyrogaUate of Alumina. — The solution of hydrate of alamina in 
the aqneoos acid is crystal 1 isab le ; tastes very roughj reddens litmns 
more stron^ifly than the acid alone; becomes turbid every time it is heated 
and clear ag^n on cooling; and forms an abundant precipitate with 
gelatin. (Braconnot.) 

The acid imparts a yellow colour to chloride of titani'um mixed with 
acetate of ammonia, and tlicn forms a brownish precipitate with it —It 
colours uranie acetate red-brown, and afterwards throws down a brown 
precipitate. — It does not after the following salts either pure or mixed 
with acetate of ammonia : SaquiMoride of chromium, sulphate of man- 
ganeu, sulphate of xitic, proto-»ulph(Ue of iron, sulphate of toball or 
sulphate of nickd. (Om.) 

The acid forms a white precipitate with tartar-emetic, colours nitrate 
of bismuth yellow, and «oon forms a thick brownish yellow precipitate; 
with protocJUoride of tin, it yields an abundance of white flakes. (Gm.) 

PffrOffoUale of Lead. — j. Sexlasic, — Obtained by digesting & with 
strong ammonia. (Berzelins.) 

b, Bii>asic. — The precipitate obtained by mixing a solution of pyro- 
^ hllate of ammonia in warm water with a ooiling solution of nitrate of 
ead, forms, after washing and drying out of contact with the air, a 
greyish white c^stalline powder, which turns brown after being exposed 



lea 



to the air for a few days. (Berzelias.) 






Salt a. 




Bendiui. 


dH'O* 126 .. 

6 PbO _ 672 .. 


.. 15-79 
.. 84-21 .. 


B4-08 


ePbCCH-O* 793 .. 


.. 100-00 




Salit. 




Bcnclim. 


C"H'0* ...- 126 

2 PbO 224 


.... 360 
.... 64-0 .. 


63-5 



2PbO,C>ni'0» 3S0 .... 100-0 

The Icad-wIt obtained lif PeloQM eiliibltMl a oonpoiitioa Mrrespouding wUi tkst 
of the >nlt b. 

C. Setquibatic. • — The scid fomn ■ pTcdpltate witli icetale of lead, and, on tddt- 
tJon of .mmonia, riso with the nitr.ie. (Gm.) — The precipitate obtained by 
mixing tlie aaneous acid at the ordinary temperature with excess of 
acetate of lead, after being quickly washed out of contact with the air, 
tlicn pressed between paper, aud dried in vacuo, is white, with a tinge 
of yellow, (Stcnhouso.) 

VOL. XI. * ^ 



bj 

also in the herb of Ddphmium eomoUda ooUected after flowering. 
(Wieke, Ann. PHarm. BO, 98.) 

Formation. 1. B7 heating citric a^ud for a ahort time. (Dahlstriini, 
pr.Chmi. 14, 855j Craeflo, Banp.) — " " ' ' * ' 

chloride of aoonitjrl (p. 404). (PeW.) 



Preparation. 1. From Aeonittan Jfapellia. — The dirty white 
mnolaF aconitate of lime which is deposited from the extract of the 
Serb, is waehed with water and alcohol, and dissohed in water containing 
ft little nitric aeidj the filtrate precipitated with acetate of lead; the 
piecipttate well washed, aospended in water and decompoeed by sDlphn- 
retted hydrogen; the traDBpatent, colonileBs Bltrate evaporatea over the 
water-bath; the residual white cryatalline mass diaaolred in ether; tlie 
reeulting solution of the acid filtered from admixed aconitate and a small 
quantity of phosphate of lime (the residue on the filter treated with 
acetate of lead in a similar manner yields an additional qnantity of the 
pnre acid); the ethereal solution left to evaporate; the remaining acid 
oissotved in water; and the solution evaporated in vacno. The acid ia 
then obtained in crystalline crnsta,wli!ch, before drying ehonld be washed 
with a small quantity of water to remove the adhering yellowish mother- 
liquor. (Bnohner.) A similar process is adopted by Wicke, for extracting 
the acid from Delphinium eortsoUda ; bat the colouring matter in this case 
is very difficnlt to separate. 

2. From Bquiaelum fiMviaiilt. — The expressed j nice is decanted from 
the green sediment, and precipitated with acetate of lead; the oopions 
grey precipitate washed witn dilute sulphuric acid and mixed with gelatin 
to precipitate the tannin ; the filtrate saturated with carbonate of lime; the 
solution evaporated to a syrup, which when left at rest, deposits malate 
of lime; the liquid separated therefrom decomposed with acetate of lead; 
the pale grey precipitate decomposed by sulpharic acidj and the filtrate 
carefully evaporated, and then set aside. In this manner brownish crnsts 
are obtained, which may be purified by repeated crystallisation, treatment 
with animal charcoal, and solution in ether. (Banp.) 

3. From Citric acid. — The acid ts melted till an empyreumatio 
odonr becomes perceptible and a mass remuoa which is rltreons after 
cooling. (Liebig, ^nn. PAarm. 26,131.) The debrdrated acid is melted 
at 155 , or the bihydrated acid kept in a state of ^ion till it assnioes a 
brownish yellow colour. ^Wackenroder.) — 85 granunes of citric acid 
are heated in a retort as quickly as the frothing permits, tilt water and 
afterwards acetone are evolved, together with carbonic oxide ras, and 
begin to rnn down the neck of the retori.; the residue when cold dissolved 
id a small quantity of water, and the solation evaporated till it forms a 
saline crnst; the mass which solidifies on cooling exhausted with ether; 
the ethereal solution filtered from the citric acid, the greater part of 
which remains nndecomposed; the aconitic acid still containing a certain 
portion of citric acid, which remains after the evaporation of the ether, 
dissolved in 5 pta. of absolute alcohol; the solution saturated with dry 
hydrochloric acid gas, which converts only the aconitic acid into a com- 
pound ether; this ether precipitated by water in the form of a heavy oil, 
and decomposed by alcoholic potash, after separation from the watery 
mixtorq; tiie resuting aconitate of potash dissolved iu water and 

202 



soiae time. When treated with crater, it repioduoes aoonitja acid. 
(Pebal.) 1, 

CombinatioTu. (I) diswlvefl very readily in water, either cold of 
hot (Buchuer); (!) dissolves in 3 pte. of water at 15°, and in a Bmaller 
quantity of hot water (Baup); (3) is easily solnble. (CraaBo.) The aoid 
from delphisiam is also very solnble in water. (Wicke.) The aolution is 
Tery mnoh inclined to effloresce during evaporation, 

AconilaU of Ammonia. — a. Trihatk. — Vfhwi prepared with the 
acid (2), it is not crystallisable. (Baup.) — The acid (I) snpersatnrated 
with ammonia and evaporated in vacuo leaves [with lose of ammonia ?j 
a clear, viscid mass which however reddens litmos. (Buohner.) 

b. SHatie, — Needles nnited in warty maases, having a pleasant 
saline and slightly acid taste. (Baohner.) — The mixtare of 1 pt. of the 
acid (2) neutralised with ammonia, with ] pt. of the free aoid, yields, by 
very gentle evaporation, crusts consisting of microscopic needles, which 
may be dried, first oa bibulooe paper under a bell-jar containing moist 
Air, and then in the open air. The salt dissolves in water more readil7 
than the salt c, bat is resolved, immediately after solution, into the salt 
c which precipitates in the pnlrornlent form, and the salts a and b, which 
remain in solution. Ttcontmns 12*53 percent, of ammonia. (Banp.) 

e. Mofiobaiie. — 1 part of the acid is neutralised with ammonia, and 
2 pte. more of add added. Nodnles, and by slow crystallisation, trans- 
parent Uminis. Dissolves in 6^ pts, of water at 15 , and in a smaller 
quantity of hot water. Contains 8*84 p. c ammonia. (Banp.) Therefore 
C'»H*(NH*)0»'. 

AconitaUiif Potcuh.- — a. Tribatic. — Qnmmr, having a not Qnplea> 
Bant saline taste, neutral, t>ecoming moist. (Bncnner.) 

6. Bibanic. — The solution of the salt a mixed with only so much 
acid as to leave a portion of that salt unaltered, is left to crystallise, the 
mother-liqaor containing the salt a being continually mixed with addi- 
tional quantities of acid. When ] pt. of the acid is neutralised with 
potash, another 1 pt. of acid added, and the liquid evaporated to the 
crystallising point, crystals are at first formed conluning more acid than 
the salt b, and afterwards the salt ( is deposited from the mother-liquor. 
— Transparent, four-sided tables, permanent in the air, or very fiat 
prisms containing 29'16 per cent, of potash. Ai Baup baa not determined 
tlie amount of water, his itntement that tbc ult u KO, 2C<UO',2HO, cuitiat 
be rceeived without further confirmation. The same remark applicB to tbe otber 
■coDitttei, >!1 of whicb be supposes to contain MO, ZC^HC + SHO, Cbit is to sajr 3 At. 
base to 2 At. add (CH^O'^), and not 2:1.— The salt dissolves in water more 
readily than c, bat is then immediately resolved into the salt c, which, if 
from 3 to 4 pta. of water are present, is precipitated as a crystalline 
powdor, and the salts a and b which remain in solution. (Baup.) 

e. Monobatic. — 1 pt of the acid neutralised with potash and mixed 
with 2 pts. more of acid, yields small trnnaparent lamiiiie united in con- 
centric groups, which aher a while become opnque, without loss of 
weight, and may likewise be heated without loss to 100°, and even till 
they begin to turn yellow. They contain 22*40 per cent, of potash, and 
are therefore KO,3C5*HO>,2HO [= CH'KO"]. They dissolve in 11 pts. 
of water at 15°, in a smaller qnantity of hot water; the solution tunii 
yellow when boiled and fields yellowish crystals. (Baup.) 



ACONmC ACID. . 40T 

AconUate of Lead. ^--^ Tribcuic. — The acid and its soda-salt form, 
with acetate of lead^ a white, finely floccalent, non-crystallising precipi- 
tate^ which, after drying over oil ot yitriol at the ordinary temperature, 
gives off 5-15 p. c. J^ At. f] water at 140°, and then contains 68*85 p. c. 
oxide of lead [C"IPPbH)"' j it may be heated to 1 50° without decompo- 
sition, and when boiled with water, contracts to a certain extent, and 
dissolves but very sparingly; the solution does not yield crystals on 
cooling. (Buchner.) The acid does not precipitate nitrate of lead till 
partially peutralised. (Banp.) 

Tlie aoid imparts a reddish colour to ferric salts, and alkaline aoonitates added te 
solations of these salts, throw down reddish gelatinous flakes. . (Buohnef , B%up.) 

Oupric AeonUaU, — The beautiful green solution of cupric carbonate 
in the aqueous acid yields a blue-green crystalline mass when evaporated. 
The solution, when boiled, deposits part of the copper in the form of 
brown-red cuprous oxide, whilst the other portion remains dissolved in 
the acid altered by oxidation. (Buchner.) 

Mercurous Aconitate, — The aoid (Baup), and its soda-salt (Buchner), 
form a white precipitate with mercnrous nitrate. 

Jiercui'ic Aconitate,'^' The solution of mercuric aconitate in the warm 
acid yields on. evaporation a white sparingly soluble powder; when boiled 
for some time, it decomposes and turns grey. (Buchner.) 

Aconitate of Silver, — Aconitate of ammonia precipitates nitrate of 
silver (Buchner); but the free acid does not; at all eyents, partial neu- 
tralisation of the acid is necessary to insure precipitation. (Baup.) The 
white pulverulent precipitate (soft, according to Liebig), blackens on 
exposure to light In the dry state, it may be heated without alteration 
to 150°, but then explodes with violence, giving off brown vapours, and 
leaving silver containing charcoal; but when moist, it decomposes even 
at 100°, the silver bein^ reduced in the form of a black powder. 
(Buchner.) When heated, it bums with a kind of detonation, and 
throws out cauliflower-like excrescences. (Liebig, Crasso.) When boiled 
with water, it is converted, without formation of gas« into ' a sparixigly 
soluble compound of silver-oxide with a peculiar crystallisable acid. The 
unaltered precipitate likewise dissolves sparingly m water; it dissolves 
readily in alcohol and ether, and effloresces therefrom in dendritic forms 
when. evaporated. (Buchner.) 

liebig. Buchner. Crasso. Wicke. 



3 H 


• 72 .••« 14*o4 ..•■• 

3 .... 0-61 


... 14-60 
... 1-00 
... 6707 
... 17-33 


.... 14-85 
.... 0-68 
.... 69-51 
.... 14-96 


.... 14-71 
.... 0-69 


3 Ago 

9 


348 .... 70-30 

72 .... 14-55 


.... 69-21 
.... 15-39 



C#«57 



CWH»Ag»0» .... 495 .... 10000 lOO'OO .... lOO'OO .... lOO'OO 

The acid dissolves readily in alcohol and eAer (Crasso); ii| 2 pts. of 
98 per cent, alcohol of 12^ ^Baup.) 



ACONITO-BUNIL. 409 

Dried over 0U qf vUrioL PebaL 

24 C 144 .... 62-34 62-18 .... 62-32 

N 14 .... 606 .... 6-02 

9H 9 .... 3-90 416 .... 4-05 

8 64 .... 27-70 .... 27-61 

C?*NH»0» 231 .... 100-00 100-00 

- C"NH7 + C^EH)^ - 4H0. * 

The add yields by combostion 30-42 yol. CO* to 1-26 vol. N, or 24*1 toL CO* 
to 1 ToL N. 

The acid dissolyee sparingly in wcUeVf easily in alcohol, and very easily 
in dilate aqueoas ammonia^ forming a purple solution. 

Silver-salt, C^NH^AgO*. — Nitrate of silver added to the ammo- 
niaoal solution of the acid, throws down rose-coloured flakes, which, when 
washed with water, pressed between paper, and dried over oil of vitriol, 
contain 31*83 p. a silver. 

"When the liquid formed by the action of pentachloride of phosphoroa on citranilic 
acid, and containing the chlorine compoand C^'*NIi'*0'Cl, is mixed^ drop by drop, with 
aniline, and the prodnct exhausted with alcohol, a yellow powder is obtained, which, 
when recrystalliaed from hot alcohol, yields crystals of aconitobianil : 

C«NH«0«C1 + CMNH7 = C»N»H"0« + HCL 



v. Aconito-bianiL 

C»N»H"0« = (?*(C»H»0*)N«H*,0». i 
L. PebaIi. Ann. Pharm. 98, 79« 

PhenyUaamitimide, 

Fojfnation and Freparation* 1« By the action of aconitic acid upon 
aniline : 

CMH«OW + 2Ci2NHy « C»N«H"0« + 6H0. 

1 At aconitic acid is heated with 3 At. aniline to 130° or 140°; and the 
resulting soft mass is boiled with dilate hydrochloric acid to remove 
excess of aniline; then left to cool; pulverised; digested for some time 
with cold dilate hydrochloric acid ; washed on a filter with water ; 
pressed, and finally treated with cold alcohoL A brown-red solation is 
then formed which leaves a brown amorphoas mass (aconitalinide?) when 
evaporated, and a yellow residue is left, which dissolves in a large quan- 
tity of boiling alcohol, and on cooling yields straw-yellow needles of 
aconito-bianil. — 2. By the action of oxychloride of citryl on aniline : 

C»H80»2CP + 2CJ2NH7 = C»N2H"0« + OHO + 2HC1. 

Aniline added in drops to oxychloride of citryl, acts with great violence, 
i'ormiu^ black products of decomposition. Bat when the oxychloride is 
Bpriukled in fine powder and by small portions into aniline, the mass being 



CAPROBVB. 411 

When meoonie of comenic acid is subjected to dry distillation^ para- 

comenic acid sublimes after the pjromeeonie aoid^ in rerj small quantity 

clucL in fei^tborj crystals | it is best obtained in Mohr*6 benzoic acid 

Apparatus at a beat not quite ^ufficiei^t to cl^ar the paper. At this 

temperature, the greater portion of the pyromeconic acid is destroyed or 

'volatilised, while in the cup and on the paper cover, there are deposited, 

slogr^iher with a small quantity of pyrum^onic aisid) dark yellow crystals 

of paracomenic acid, which, by splutiofi in hot water, boiling with ftplmal 

charcoal, filtration and cooling, i^re cQB?erted into hard crystalline gr^ps 

of a very pale ye